EP2947090A1 - Novel monophosphite ligands with a tertiary butyloxycarbonyl group - Google Patents

Novel monophosphite ligands with a tertiary butyloxycarbonyl group Download PDF

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EP2947090A1
EP2947090A1 EP15166027.1A EP15166027A EP2947090A1 EP 2947090 A1 EP2947090 A1 EP 2947090A1 EP 15166027 A EP15166027 A EP 15166027A EP 2947090 A1 EP2947090 A1 EP 2947090A1
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alkyl
aryl
ligand
butyl
coo
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German (de)
French (fr)
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EP2947090B1 (en
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Katrin Marie DYBALLA
Robert Franke
Dieter Hess
Dirk Fridag
Frank GEILEN
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Evonik Operations GmbH
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Evonik Industries AG
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    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07F—ACYCLIC, CARBOCYCLIC OR HETEROCYCLIC COMPOUNDS CONTAINING ELEMENTS OTHER THAN CARBON, HYDROGEN, HALOGEN, OXYGEN, NITROGEN, SULFUR, SELENIUM OR TELLURIUM
    • C07F9/00—Compounds containing elements of Groups 5 or 15 of the Periodic System
    • C07F9/02—Phosphorus compounds
    • C07F9/06—Phosphorus compounds without P—C bonds
    • C07F9/08—Esters of oxyacids of phosphorus
    • C07F9/141—Esters of phosphorous acids
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J31/00—Catalysts comprising hydrides, coordination complexes or organic compounds
    • B01J31/16—Catalysts comprising hydrides, coordination complexes or organic compounds containing coordination complexes
    • B01J31/18—Catalysts comprising hydrides, coordination complexes or organic compounds containing coordination complexes containing nitrogen, phosphorus, arsenic or antimony as complexing atoms, e.g. in pyridine ligands, or in resonance therewith, e.g. in isocyanide ligands C=N-R or as complexed central atoms
    • B01J31/1845—Catalysts comprising hydrides, coordination complexes or organic compounds containing coordination complexes containing nitrogen, phosphorus, arsenic or antimony as complexing atoms, e.g. in pyridine ligands, or in resonance therewith, e.g. in isocyanide ligands C=N-R or as complexed central atoms the ligands containing phosphorus
    • B01J31/185—Phosphites ((RO)3P), their isomeric phosphonates (R(RO)2P=O) and RO-substitution derivatives thereof
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J31/00—Catalysts comprising hydrides, coordination complexes or organic compounds
    • B01J31/16—Catalysts comprising hydrides, coordination complexes or organic compounds containing coordination complexes
    • B01J31/22—Organic complexes
    • B01J31/2204—Organic complexes the ligands containing oxygen or sulfur as complexing atoms
    • B01J31/2208—Oxygen, e.g. acetylacetonates
    • B01J31/2221—At least one oxygen and one phosphorous atom present as complexing atoms in an at least bidentate or bridging ligand
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C45/00—Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds
    • C07C45/49—Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds by reaction with carbon monoxide
    • C07C45/50—Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds by reaction with carbon monoxide by oxo-reactions
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C45/00—Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds
    • C07C45/49—Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds by reaction with carbon monoxide
    • C07C45/50—Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds by reaction with carbon monoxide by oxo-reactions
    • C07C45/505—Asymmetric hydroformylation
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07F—ACYCLIC, CARBOCYCLIC OR HETEROCYCLIC COMPOUNDS CONTAINING ELEMENTS OTHER THAN CARBON, HYDROGEN, HALOGEN, OXYGEN, NITROGEN, SULFUR, SELENIUM OR TELLURIUM
    • C07F15/00—Compounds containing elements of Groups 8, 9, 10 or 18 of the Periodic System
    • C07F15/0006—Compounds containing elements of Groups 8, 9, 10 or 18 of the Periodic System compounds of the platinum group
    • C07F15/0073—Rhodium compounds
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07F—ACYCLIC, CARBOCYCLIC OR HETEROCYCLIC COMPOUNDS CONTAINING ELEMENTS OTHER THAN CARBON, HYDROGEN, HALOGEN, OXYGEN, NITROGEN, SULFUR, SELENIUM OR TELLURIUM
    • C07F9/00—Compounds containing elements of Groups 5 or 15 of the Periodic System
    • C07F9/02—Phosphorus compounds
    • C07F9/06—Phosphorus compounds without P—C bonds
    • C07F9/08—Esters of oxyacids of phosphorus
    • C07F9/141—Esters of phosphorous acids
    • C07F9/145—Esters of phosphorous acids with hydroxyaryl compounds
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07F—ACYCLIC, CARBOCYCLIC OR HETEROCYCLIC COMPOUNDS CONTAINING ELEMENTS OTHER THAN CARBON, HYDROGEN, HALOGEN, OXYGEN, NITROGEN, SULFUR, SELENIUM OR TELLURIUM
    • C07F9/00—Compounds containing elements of Groups 5 or 15 of the Periodic System
    • C07F9/02—Phosphorus compounds
    • C07F9/547—Heterocyclic compounds, e.g. containing phosphorus as a ring hetero atom
    • C07F9/6564—Heterocyclic compounds, e.g. containing phosphorus as a ring hetero atom having phosphorus atoms, with or without nitrogen, oxygen, sulfur, selenium or tellurium atoms, as ring hetero atoms
    • C07F9/6571—Heterocyclic compounds, e.g. containing phosphorus as a ring hetero atom having phosphorus atoms, with or without nitrogen, oxygen, sulfur, selenium or tellurium atoms, as ring hetero atoms having phosphorus and oxygen atoms as the only ring hetero atoms
    • C07F9/6574—Esters of oxyacids of phosphorus
    • C07F9/65742—Esters of oxyacids of phosphorus non-condensed with carbocyclic rings or heterocyclic rings or ring systems
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07F—ACYCLIC, CARBOCYCLIC OR HETEROCYCLIC COMPOUNDS CONTAINING ELEMENTS OTHER THAN CARBON, HYDROGEN, HALOGEN, OXYGEN, NITROGEN, SULFUR, SELENIUM OR TELLURIUM
    • C07F9/00—Compounds containing elements of Groups 5 or 15 of the Periodic System
    • C07F9/02—Phosphorus compounds
    • C07F9/547—Heterocyclic compounds, e.g. containing phosphorus as a ring hetero atom
    • C07F9/6564—Heterocyclic compounds, e.g. containing phosphorus as a ring hetero atom having phosphorus atoms, with or without nitrogen, oxygen, sulfur, selenium or tellurium atoms, as ring hetero atoms
    • C07F9/6571—Heterocyclic compounds, e.g. containing phosphorus as a ring hetero atom having phosphorus atoms, with or without nitrogen, oxygen, sulfur, selenium or tellurium atoms, as ring hetero atoms having phosphorus and oxygen atoms as the only ring hetero atoms
    • C07F9/6574—Esters of oxyacids of phosphorus
    • C07F9/65744—Esters of oxyacids of phosphorus condensed with carbocyclic or heterocyclic rings or ring systems
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J2231/00—Catalytic reactions performed with catalysts classified in B01J31/00
    • B01J2231/30—Addition reactions at carbon centres, i.e. to either C-C or C-X multiple bonds
    • B01J2231/32—Addition reactions to C=C or C-C triple bonds
    • B01J2231/321—Hydroformylation, metalformylation, carbonylation or hydroaminomethylation
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J2531/00—Additional information regarding catalytic systems classified in B01J31/00
    • B01J2531/80—Complexes comprising metals of Group VIII as the central metal
    • B01J2531/82—Metals of the platinum group
    • B01J2531/822—Rhodium
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J2540/00—Compositional aspects of coordination complexes or ligands in catalyst systems
    • B01J2540/10—Non-coordinating groups comprising only oxygen beside carbon or hydrogen

Definitions

  • the invention relates to novel monophosphite ligands having a tert- butyloxycarbonyl group (BOC group), their use as ligands in the hydroformylation and the hydroformylation process.
  • BOC group tert- butyloxycarbonyl group
  • Each catalytically active composition has its specific advantages. Depending on the starting material and target product therefore different catalytically active compositions are used.
  • Rhodium monophosphite complexes in catalytically active compositions are suitable for the hydroformylation of branched olefins having internal double bonds.
  • EP 0 155 508 is the use of bisarylene-substituted monophosphites in the rhodium-catalyzed hydroformylation of sterically hindered olefins, e.g. As isobutene known.
  • sterically hindered olefins e.g. As isobutene known.
  • very high rhodium concentrations eg 250 ppm
  • TDTBPP tris (2,4-di-tert-butylphenyl) phosphite
  • the technical problem underlying the present invention is to provide a novel monophosphite ligand which is useful in the hydroformylation of unsaturated Compounds does not have the disadvantages previously shown in the prior art.
  • the production cost should be lower than that of the phosphonite ligands described above, on the other hand, a good n-selectivity with respect to the hydroformylation should be achieved.
  • the new monophosphite ligands should also be suitable for the oxidation of technical olefin mixtures which contain mainly branched olefins with internal double bonds. During the oxification, a high proportion of desired terminally hydroformylated products should be obtained.
  • the object is achieved by a ligand according to claim 1.
  • - (C 1 -C 12 ) -alkyl comprises straight-chain and branched alkyl groups. Preferably, these are unsubstituted straight-chain or branched - (C 1 -C 8 ) -alkyl and most preferably - (C 1 -C 6 ) -alkyl groups.
  • Examples of - (C 1 -C 12 ) -alkyl groups are, in particular, methyl, ethyl, propyl, isopropyl, n-butyl, ido-butyl, sec-butyl, tert-butyl, n-pentyl, 2-pentyl, 2- Methylbutyl, 3-methylbutyl, 1,2-dimethylpropyl, 1,1-dimethylpropyl, 2,2-dimethylpropyl, 1-ethylpropyl, n-hexyl, 2-hexyl, 2-methylpentyl, 3 Methylpentyl, 4-methylpentyl, 1,1-dimethylbutyl, 1,2-dimethylbutyl, 2,2-dimethylbutyl, 1,3-dimethylbutyl, 2,3-dimethylbutyl, 3,3-dimethylbutyl, 1,1,2-trimethylpropyl, 1,2,2-trimethylpropyl, 1-
  • Substituted - (C 1 -C 12 ) -alkyl groups and substituted - (C 1 -C 12 ) -alkoxy groups may, depending on their chain length, have one or more substituents.
  • the substituents are preferably selected independently of one another from - (C 3 -C, 2 ) -cycloalkyl, (C 3 -C 12 ) -heterocycloalkyl, - (C 6 -C 20 ) -aryl, fluorine, chlorine, cyano, formyl, acyl or alkoxycarbonyl,
  • the term - (C 3 -C 12 ) -cycloalkyl encompasses mono-, bi- or tricyclic hydrocarbon radicals having 3 to 12, in particular 5 to 12, carbon atoms. These include cyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl, cycloheptyl, cyclooctyl, cyclododecyl, cyclopentadecyl, norbonyl or adamantyl.
  • - (C 3 -C 12 ) -heterocycloalkyl groups for the purposes of the present invention comprises non-aromatic, saturated or partially unsaturated cycloaliphatic groups having 3 to 12, in particular 5 to 12, carbon atoms.
  • the - (C 3 -C 12 ) -heterocycloalkyl groups preferably have 3 to 8, more preferably 5 or 6, ring atoms.
  • the ring carbon atoms are replaced by heteroatoms or heteroatom-containing groups.
  • - (C 3 -C 12 ) -heterocycloalkyl groups include tetrahydrothiophenyl, tetrhydrofuryl, tetrahydropyranyl and dioxanyl.
  • Substituted - (C 3 -C 12 ) -cycloalkyl groups and substituted - (C 3 -C 12 ) -heterocycloalkyl groups may, depending on their ring size, have one or more (eg 1, 2, 3, 4 or 5) further substituents.
  • substituents are preferably independently selected from - (C 1 -C 12 ) -alkyl, - (C 1 -C 12 ) -alkoxy, - (C 3 -C 12 ) -cycloalkyl, - (C 3 -C 12 ) - Heterocycloalkyl, - (C 6 -C 20 ) -aryl, fluorine, chlorine, cyano, formyl, acyl or alkoxycarbonyl.
  • Substituted - (C 3 -C 12 ) -cycloalkyl groups preferably carry one or more - (C 1 -C 6 ) -alkyl groups.
  • Substituted - (C 3 -C 12 ) -heterocycloalkyl groups preferably carry one or more - (C 1 -C 6 ) -alkyl groups.
  • - (C 6 -C 20 ) -aryl and - (C 6 -C 20 ) -aryl (C 6 -C 20 ) -aryl encompasses in the context of the present invention mono- or polycyclic aromatic hydrocarbon radicals. These have 6 to 20 ring atoms, particularly preferably 6 to 14 ring atoms, in particular 6 to 10 ring atoms, on.
  • Aryl is preferably - (C 6 -C 10 ) -aryl and - (C 6 -C 10 ) -aryl (C 6 -C 10 ) -aryl.
  • Aryl is especially phenyl, naphthyl, indenyl, fluorenyl, anthracenyl, phenanthrenyl, naphthacenyl, chrysenyl, pyrenyl, coronenyl.
  • aryl is phenyl, naphthyl and antracenyl.
  • Substituted - (C 6 -C 20 ) -aryl groups and - (C 6 -C 20 ) -aryl (C 6 -C 20 ) -aryl groups can, depending on the ring size, one or more (eg 1, 2, 3 , 4 or 5) have substituents.
  • substituents are preferably independently selected from --H, - (C 1 -C 12 ) -alkyl, -O- (C 1 -C 12 ) -alkyl, -O- (C 6 -C 20 ) -aryl, - ( C 6 -C 20 ) -aryl, -halogen (such as Cl, F, Br, I), -COO- (C 1 -C 12 ) -alkyl, -CONH- (C 1 -C 12 ) -alkyl, - ( C 6 -C 20 ) -aryl-CON [(C 1 -C 12 ) -alkyl] 2 , -CO- (C 1 -C 12 ) -alkyl, -CO- (C 6 -C 20 ) -aryl, COOH, -OH, -SO 3 H; -SO 3 Na, -NO 2 , -CN, -NH 2 , -N [(C 1 -
  • Substituted - (C 6 -C 20 ) -aryl groups and - (C 6 -C 20 ) -aryl (C 6 -C 20 ) -aryl groups are preferably substituted - (C 6 -C 10 ) -aryl groups and - (C 6 -C 10 ) aryl- (C 6 -C 10 ) -aryl groups, in particular substituted phenyl or substituted naphthyl or substituted anthracenyl.
  • Substituted - (C 6 -C 20 ) -aryl groups preferably carry one or more, for example 1, 2, 3, 4 or 5 substituents selected from - (C 1 -C 12 ) -alkyl groups, - (C 1 -C 12 ) - alkoxy groups.
  • Z stands for:
  • X and Y are the same radicals.
  • R 3 and R 6 are -O- (C 1 -C 12 ) -alkyl.
  • R 3 and R 6 are -OMe.
  • R 1 and R 8 are - (C 1 -C 12 ) alkyl.
  • R 1 and R 8 are tert -butyl.
  • R 1 , R 3 , R 6 and R 8 are - (C 1 -C 12 ) -alkyl.
  • R 1 , R 3, R 6 and R 8 are methyl.
  • R 1 , R 3, R 6 and R 8 are tert -butyl.
  • R 1 , R 2 , R 3 , R 4 , R 5 , R 6 , R 7 and R 8 are -H.
  • R 11 and R 14 are -O- (C 1 -C 12 ) -alkyl.
  • R 11 and R 14 are -OMe.
  • R 9 and R 16 are - (C 1 -C 12 ) alkyl.
  • R 9 and R 16 are tert -butyl.
  • R 9 , R 11 , R 14 and R 16 are - (C 1 -C 12 ) -alkyl.
  • R 9 , R 11 , R 14 and R 16 are methyl.
  • R 9 , R 11 , R 14 and R 16 are tert -butyl.
  • R 9 , R 10 , R 11 , R 12 , R 13 , R 14 , R 15 and R 16 are -H.
  • R 11 and R 14 are -O- (C 1 -C 12 ) -alkyl.
  • R 11 and R 14 are -OMe.
  • R 9 and R 16 are - (C 1 -C 12 ) alkyl.
  • R 9 and R 16 are tert -butyl.
  • R 9 , R 11 , R 14 and R 16 are - (C 1 -C 12 ) -alkyl.
  • R 9 , R 11 , R 14 and R 16 are methyl.
  • R 9 , R 11 , R 14 and R 16 are tert -butyl.
  • R 9 , R 10 , R 11 , R 12 , R 13 , R 14 , R 15 and R 16 are -H.
  • the metal is Rh.
  • the ligand as a ligand in a ligand-metal complex for catalysing a hydroformylation reaction is claimed.
  • process steps a) to d) can be carried out in any order.
  • the reaction is carried out under usual conditions.
  • Preferred are a temperature of 80 ° C to 160 ° C and a pressure of 1 to 300 bar.
  • Particularly preferred are a temperature of 100 ° C to 160 ° C and a pressure of 15 to 250 bar.
  • the metal is Rh.
  • the educts for the hydroformylation according to the process of the invention are olefins or mixtures of olefins, in particular monoolefins having 2 to 24, preferably 3 to 16, particularly preferably 3 to 12 carbon atoms with terminal or internal CC double bonds, such as 1-propene, 1-butene, 2-butene, 1- or 2-pentene, 2-methyl-1-butene, 2-methyl-2-butene, 3-methyl-1-butene, 1, 2 or 3, -hexene, the C 6 olefin mixture (dipropene), heptene, 2- or 3-methyl-1-hexenes, octenes, 2-methylheptene, 3-methylheptene, 5-methyl-2-heptene, 6-methylene obtained in the dimerization of propene 2-heptene, 2-ethyl-1-hexene, the C 8 olefin mixture (di-n-butene, di-iso-butene), nonenes
  • ⁇ -olefins, terminally branched, internally branched and internally branched olefins can be hydroformylated using the ligands according to the invention. Noteworthy here is the high yield of terminally hydrofomylated olefin, even if only a small proportion of olefins with terminal double bond was present in the educt.
  • Nuclear resonance spectra were recorded using a Bruker Avance 300 and Bruker Avance 400, respectively, and gas chromatographic analysis on Agilent GC 7890A.
  • the ligands according to the invention can be prepared in various ways. Three possible ways are shown in the following schemes (A to C).
  • tert-butyl (3,3'-di-tert-butyl-2 '- ((dichlorophosphino) oxy) -5,5'-dimethoxy- [1 , 1'-biphenyl] -2-yl) carbonate dissolved in 100 ml of dried acetonitrile.
  • reaction conditions ligand 1, reaction temperature: 120 ° C
  • Lines 1 and 2 list attempts for rhodium-catalyzed hydroformylation of the educt cis-2-butene with ligand 1 .
  • pentanal At a pressure of 20 bar of synthesis gas, in experiment 1, 58.0 mol% pentanal are formed with a pentane selectivity of 45.3%.
  • the proportion of hydrogenation to the alkane is low at about 1.3 to 1.5%.
  • the formation of pentanol is not observed.
  • An increase in the synthesis gas pressure leads to an increase in the Pentanal yield to 95.1 mol%, the regioselectivity, however, falls to about 40%.
  • the experiments are carried out both with the ligand 1 according to the invention and with the comparison ligand TDTBPP.
  • the entries 1 to 14 respectively show results of tests at constant temperature in the range of 80 ° C to 140 ° C, respectively for the ligand 1 according to the invention as well as for the comparison ligand (TDTBPP).
  • the ligand 1 of the invention is characterized in all cases by a significantly higher n-selectivity to the desired product with very good overall yields. The formation of alkanes and alcohols is insignificant. Comparing entries 13 and 14, ligand 1 shows an almost 8% increased selectivity compared to the commercially available control ligand. Entries 15 to 17 show the use of ligand 1 with different molar excesses to rhodium. In all cases, very good n-selectivities could be achieved.
  • Table 10 gives the results for the hydroformylation of di-n-butene.
  • Table 10 contains experimental results for the rhodium-catalyzed hydroformylation of di-n-butene with the ligand 1.
  • Entries 1 to 5 were carried out at 120 ° C and 50 bar, entry 8 at 40 bar.
  • Entries 2 and 3 are a double determination with a ligand excess of 7 to rhodium and a rhodium concentration based on the total reaction mixture of 80 ppm, entry 1 was carried out at an excess of about 10: 1 and a Rh concentration of 40 ppm.
  • Entry 4 describes a reduction of the excess to 5: 1 over entries 2 and 3.
  • Entries 5 to 8 are experiments with high ligand excess of about 20: 1.
  • Entries 5 to 7 were carried out at different temperatures. Entry 8 differs from entry 5 by pressure.
  • the above table contains a summary of the experimental data for the hydroformylation of n-octenes with the ligand 3 in the form of a temperature range of 80 ° C to 120 ° C at 50 bar synthesis gas pressure, a Rh concentration of about 100 ppm and a ligand excess from about 20: 1.
  • the n-nonane selectivities are low at 4.9 to 11.9 mol% in this series of experiments, but the aldehyde yields are almost quantitative and very good at higher temperatures.
  • the alkane formation is ⁇ 1% low, the hydrogenation to alcohols is not observed.
  • Table 12 gives the results for the hydroformylation of di-n-butene.
  • Table 12 above contains experimental data for the rhodium-catalyzed hydroformylation of di-n-butene with ligands 3, 4 and 5. While ligand 4 (entry 1) provides a moderate overall yield of aldehydes and alcohols, they are characterized by ligands 3 and 4 very good yields. In particular, the ligand 5 shows at elevated temperature (140 ° C) almost quantitative conversions (entries 5 to 7).
  • the new catalyst system is also suitable for the oxidation of industrial olefin mixtures containing mainly branched olefins with internal double bonds and a high proportion of desired hydroformylated products can be obtained.
  • the monophosphite ligands according to the invention have a very good n-selectivity with respect to the hydroformylation.
  • the selectivity to the desired linear aldehydes here is significantly greater than, for example, in the commercially available ligand TDTBPP. The stated objects are thus achieved by these novel ligands according to the invention.

Abstract

Neue Monophosphitliganden mit einer tert -Butyloxycarbonyl-Gruppe, deren Verwendung als Liganden in der Hydroformylierung und das Hydroformylierungsverfahren.New monophosphite ligands with a tert-butyloxycarbonyl group, their use as ligands in hydroformylation, and the hydroformylation process.

Description

Die Erfindung betrifft neue Monophosphitliganden mit einer tert-Butyloxycarbonyl-Gruppe (BOC-Gruppe), deren Verwendung als Liganden in der Hydroformylierung und das Hydroformylierungsverfahren.The invention relates to novel monophosphite ligands having a tert- butyloxycarbonyl group (BOC group), their use as ligands in the hydroformylation and the hydroformylation process.

Die Reaktionen zwischen Olefinverbindungen, Kohlenmonoxid und Wasserstoff in Gegenwart eines Katalysators zu den um ein C-Atom reicheren Aldehyden ist als Hydroformylierung bzw. Oxierung bekannt. Als Katalysatoren in diesen Reaktionen werden häufig Verbindungen der Übergangsmetalle der VIII. Gruppe des Periodensystems der Elemente verwendet. Bekannte Liganden sind beispielsweise Verbindungen aus den Klassen der Phosphine, Phosphite und Phosphonite mit jeweils dreiwertigem Phosphor PIII. Eine gute Übersicht über den Stand der Hydroformylierung von Olefinen findet sich in B. CORNILS, W. A. HERRMANN, "Applied Homogeneous Catalysis with Organometallic Compounds", Vol. 1 & 2, VCH, Weinheim, New York, 1996 bzw. R. Franke, D. Selent, A. Börner, "Applied Hydroformylation", Chem. Rev., 2012 , DOI:10.1021/cr3001803.The reactions between olefin compounds, carbon monoxide and hydrogen in the presence of a catalyst to give the C-atom richer aldehydes is known as hydroformylation or oxination. As catalysts in these reactions, compounds of the transition metals of Group VIII of the Periodic Table of the Elements are frequently used. Known ligands are, for example, compounds from the classes of phosphines, phosphites and phosphonites, each with trivalent phosphorus P III . A good overview of the state of the hydroformylation of olefins can be found in B. CORNILS, WA HERRMANN, "Applied Homogeneous Catalysis with Organometallic Compounds", Vol. 1 & 2, VCH, Weinheim, New York, 1996 respectively. R. Franke, D. Selent, A. Börner, Applied Hydroformylation, Chem. Rev., 2012 , DOI: 10.1021 / cr3001803.

Jede katalytisch aktive Zusammensetzung hat ihre spezifischen Vorzüge. Je nach Einsatzstoff und Zielprodukt kommen daher unterschiedliche katalytisch aktive Zusammensetzungen zum Einsatz.Each catalytically active composition has its specific advantages. Depending on the starting material and target product therefore different catalytically active compositions are used.

Der Nachteil von zwei- und mehrzähnigen Phosphinliganden ist ein relativ hoher Aufwand, der zu ihrer Darstellung notwendig ist. Daher ist es oftmals nicht rentabel, solche Systeme in technischen Prozessen einzusetzen. Hinzu kommt eine vergleichsweise geringe Aktivität, die durch hohe Verweilzeiten reaktionstechnisch kompensiert werden muss. Dies wiederum führt zu unerwünschten Nebenreaktionen der Produkte.The disadvantage of bidentate and polydentate phosphine ligands is a relatively high cost, which is necessary for their presentation. Therefore, it is often not profitable to use such systems in technical processes. In addition, there is a comparatively low activity, which must be compensated by high residence times reaction technology. This in turn leads to undesirable side reactions of the products.

In Angew. Chem. Int. Ed. 2000, 39, No. 9, S.1639-1641 von Börner et al. werden Liganden beschrieben, welche eine P-C- und zwei P-O-Bindungen aufweisen, es handelt sich somit um Phosphonite. Die dort beschriebenen Phosphonite weisen bei einem Einsatz in der Hydroformylierung n/iso-Selektivitäten (n/iso = das Verhältnis von linearem Aldehyd (= n) zu verzweigtem (= iso) Aldehyd)) von 0,61 bis 1,57 auf.In Angew. Chem. Int. Ed. 2000, 39, no. 9, p.1639-1641 of Börner et al. ligands are described which have one PC and two PO bonds, thus they are phosphonites. When used in hydroformylation, the phosphonites described there have n / iso selectivities (n / iso = the ratio of linear aldehyde (= n) to branched (= iso) aldehyde)) of 0.61 to 1.57.

Die in DE 199 54 721 beschriebenen Phosphonitliganden weisen eine gute n/iso-Selektivität auf. Allerdings haben eigene Untersuchungen ergeben, dass die Verbindung II-c (in DE 199 54 721 ; Seite 6) zu einer photochemisch induzierten Zersetzung neigt, weshalb von einem großtechnischen Einsatz abzusehen ist.In the DE 199 54 721 described phosphonite ligands have a good n / iso-selectivity. However, own investigations have shown that the compound II-c (in DE 199 54 721 ; Page 6) tends to a photochemically induced decomposition, which is why one can foresee a large-scale use.

Ein Nachteil der Liganden mit einer Phosphonitstruktur besteht in der sehr aufwändigen Herstellung. Die Möglichkeit einer günstigen und einfachen Synthese spielt jedoch für den Einsatz von Liganden in einem großtechnischen Prozess aber eine elementare Rolle.A disadvantage of ligands with a phosphonite structure is the very complicated production. The possibility of a cheap and simple synthesis, however, plays an elementary role for the use of ligands in a large-scale process.

Die einfache Verfügbarkeit und damit verbunden die gute Möglichkeit eines großtechnischen Einsatzes ist ein wichtiges Kriterium, da der Herstellungsaufwand und damit verbunden die anfallenden Produktionskosten für den Liganden nur so hoch sein dürfen, dass die Rentabilität des Gesamtprozesses, in dem der Ligand später eingesetzt wird, weiterhin gewährleistet ist.The ease of availability and the associated possibility of large-scale use is an important criterion, since the production cost and associated production costs for the ligand may only be so high that the profitability of the overall process in which the ligand is used later continues is guaranteed.

Rhodium-Monophosphit-Komplexe in katalytisch aktiven Zusammensetzungen sind geeignet für die Hydroformylierung von verzweigten Olefinen mit innenständigen Doppelbindungen.Rhodium monophosphite complexes in catalytically active compositions are suitable for the hydroformylation of branched olefins having internal double bonds.

Seit den 1970er Jahren ist die Verwendung von so genannten "bulky phosphites" in der Hydroformylierung beschrieben (siehe u.a. van Leeuwen et. al, Journal of Catalysis, 2013, 298, 198-205 ). Diese zeichnen sich durch eine gute Aktivität aus, jedoch ist die n/i-Selektivität für endständig oxierte Verbindungen verbesserungswürdig.Since the 1970s, the use of so-called "bulky phosphites" in the hydroformylation has been described (see, inter alia van Leeuwen et. al, Journal of Catalysis, 2013, 298, 198-205 ). These are characterized by a good activity, however, the n / i selectivity for terminally oxidized compounds is in need of improvement.

Aus EP 0 155 508 ist die Verwendung von bisarylensubstituierten Monophosphiten bei der rhodiumkatalysierten Hydroformylierung von sterisch gehinderten Olefinen, z. B. Isobuten, bekannt. Hierbei werden jedoch z.T. sehr hohe Rhodiumkonzentrationen verwendet (u.a. 250 ppm), was in Anbetracht des derzeitigen Rhodiumpreises für ein großtechnisches Verfahren inakzeptabel ist und verbessert werden muss.Out EP 0 155 508 is the use of bisarylene-substituted monophosphites in the rhodium-catalyzed hydroformylation of sterically hindered olefins, e.g. As isobutene known. However, in some cases very high rhodium concentrations are used (eg 250 ppm), which is unacceptable and must be improved in view of the current rhodium price for a large-scale process.

Für Hydroformylierungsreaktionen ist derzeit Tris(2,4-di-tert-butylphenyl)phosphit (TDTBPP) einer der leistungsstärksten und kommerziell verfügbaren Monophosphitliganden, welcher unter dem Handelsnamen Alkanox 240 erhältlich ist (siehe auch R. Franke, D. Selent, A. Börner, "Applied Hydroformylation", Chem. Rev., 2012, 112, S.5681 Kapitel 3.4.2 ).For hydroformylation reactions, tris (2,4-di-tert-butylphenyl) phosphite (TDTBPP) is currently one of the most powerful and commercially available monophosphite ligands available under the trade name Alkanox 240 (see also US Pat R. Franke, D. Selent, A. Börner, Applied Hydroformylation, Chem. Rev., 2012, 112, p.5681, Chapter 3.4.2 ).

Die technische Aufgabe, welche der vorliegenden Erfindung zugrunde lag, ist die Bereitstellung eines neuen Monophosphitliganden, welcher in der Hydroformylierung von ungesättigten Verbindungen nicht die aus dem Stand der Technik zuvor aufgezeigten Nachteile aufweist.The technical problem underlying the present invention is to provide a novel monophosphite ligand which is useful in the hydroformylation of unsaturated Compounds does not have the disadvantages previously shown in the prior art.

Zum einen soll der Herstellungsaufwand geringer sein als der bei den oben beschriebenen Phosphonitliganden, zum anderen soll eine gute n-Selektivität in Bezug auf die Hydroformylierung erzielt werden.On the one hand, the production cost should be lower than that of the phosphonite ligands described above, on the other hand, a good n-selectivity with respect to the hydroformylation should be achieved.

Insbesondere sollen die neuen Monophosphitliganden auch zur Oxierung von technischen Olefingemischen, die hauptsächlich verzweigte Olefine mit innenständigen Doppelbindungen enthalten, geeignet sein. Bei der Oxierung soll hierbei ein hoher Anteil an gewünschten endständig hydroformylierten Produkten erhalten werden.In particular, the new monophosphite ligands should also be suitable for the oxidation of technical olefin mixtures which contain mainly branched olefins with internal double bonds. During the oxification, a high proportion of desired terminally hydroformylated products should be obtained.

Die Aufgabe wird gelöst durch einen Liganden nach Anspruch 1.The object is achieved by a ligand according to claim 1.

Ligand, welcher eine der beiden allgemeinen Strukturen I oder II aufweist:

Figure imgb0001
Figure imgb0002
 wobei
R1, R2, R3, R4, R5, R6, R7, R8 jeweils unabhängig voneinander ausgewählt sind aus: -H, -(C1-C12)-Alkyl, -O-(C1-C12)-Alkyl, -O-(C6-C20)-Aryl, -(C6-C20)-Aryl, Halogen (wie Cl, F, Br, I), COO-(C1-C12)-Alkyl, CONH-(C1-C12)-Alkyl, -(C6-C20)-Aryl-CON[(C1-C12)-Alkyl]2, -CO-(C1-C12)-Alkyl,-CO-(C6-C20)-Aryl,-COOH, -OH, -SO3H; -SO3Na, -NO2, -CN, -NH2; -N[(C1C12)-Alkyl]2;
X und Y jeweils unabhängig voneinander ausgewählt sind aus:

  • -(C1-C12)-Alkyl, -(C6-C20)-Aryl, -(C6-C20)-Aryl-(C1-C12)-Alkyl, -(C6-C20)-Aryl-O-(C1-C12)-Alkyl, -(C1-C12)-Alkyl-(C6-C20)-Aryl, -(C6-C20)-Aryl-COO-(C1-C12)-Alkyl, -(C6-C20)-Aryl-CONH-(C1-C12)-Alkyl,-(C6-C20)-Aryl-CON[(C1-C12)-Alkyl]2, -(C4-C20)-Heteroaryl, -(C4-C20)-Heteroaryl-(C1-C12)-Alkyl,-(C5-C8)-Cycloalkyl, -(C6-C20)-Aryl-CO-(C6-C20)-Aryl,
Z ausgewählt ist aus:
  • -(C1-C12)-Alkyl-, -(C6-C20)-Aryl-, -(C6-C20)-Aryl-(C1-C12)-Alkyl-, -(C1-C12)-Alkyl-(C6-C20)-Aryh -(C4-C20)-Heteroaryl-, -(C6-C20)-Aryl-CO-(C6-C20)-Aryl-, -(C6-C20)-Aryl-(C6-C20)-Aryl-;
wobei die genannten Alkyl-, Heteroalkyl-, Cycloalkyl-, Heterocycloalkyl-, Aryl- und Heteroarylgruppen substituiert sein können.
(C1-C12)-Alkyl und O-(C1-C12)-Alkyl können jeweils unsubstituiert oder durch einen oder mehrere gleiche oder verschiedene Reste substituiert sein, die ausgewählt sind unter (C3-C12)-Cycloalkyl, (C3-C12)-Heterocycloalkyl, (C6-C20)-Aryl, Fluor, Chlor, Cyano, Formyl, Acyl oder Alkoxycarbonyl.
(C3-C12)-Cycloalkyl und (C3-C12)-Heterocycloalkyl können jeweils unsubstituiert oder durch einen oder mehrere gleiche oder verschiedene Reste substituiert sein, die ausgewählt sind unter (C1-C12)-Alkyl, (C1-C12)-Alkoxy, (C3-C12)-Cycloalkyl, (C3-C12)-Heterocycloalkyl, (C6-C20)-Aryl, Fluor, Chlor, Cyano, Formyl, Acyl oder Alkoxycarbonyl.
(C6-C20)-Aryl und -(C6-C20)-Aryl-(C6-C20)-Aryl- können jeweils unsubstituiert oder durch einen oder mehrere gleiche oder verschiedene Reste substituiert sein, die ausgewählt sind unter -H, -(C1-C12)-Alkyl, -O-(C1-C12)-Alkyl, -O-(C6-C20)-Aryl, -(C6-C20)-Aryl, -Halogen (wie Cl, F, Br, I), -COO-(C1-C12)-Alkyl, -CONH-(C1-C12)-Alkyl, -(C6-C20)-Aryl-CON[(C1-C12)-Alkyl]2, -CO-(C1-C12)-Alkyl, -CO-(C6-C20)-Aryl, -COOH, -OH, -SO3H; -SO3Na, -NO2, -CN, -NH2, -N[(C1-C12)-Alkyl]2.Ligand which has one of the two general structures I or II :
Figure imgb0001
Figure imgb0002
 in which
R 1 , R 2 , R 3 , R 4 , R 5 , R 6 , R 7 , R 8 are each independently selected from: -H, - (C 1 -C 12 ) -alkyl, -O- (C 1 -C 12 ) -alkyl, -O- (C 6 -C 20 ) -aryl, - (C 6 -C 20 ) -aryl, halogen (such as Cl, F, Br, I), COO- (C 1 -C 12 ) -alkyl, CONH- (C 1 -C 12 ) -alkyl, - (C 6 -C 20 ) -aryl-CON [(C 1 -C 12 ) -alkyl] 2 , -CO- (C 1 -C 12 ) -alkyl, -CO- (C 6 -C 20 ) -aryl, -COOH, -OH, -SO 3 H; -SO 3 Na, -NO 2 , -CN, -NH 2 ; -N [(C 1 C 12 ) -alkyl] 2 ;
X and Y are each independently selected from:
  • - (C 1 -C 12 ) -alkyl, - (C 6 -C 20 ) -aryl, - (C 6 -C 20 ) -aryl (C 1 -C 12 ) -alkyl, - (C 6 -C 20 ) -Aryl-O- (C 1 -C 12 ) -alkyl, - (C 1 -C 12 ) -alkyl- (C 6 -C 20 ) -aryl, - (C 6 -C 20 ) -aryl-COO- (C 1 -C 12 ) -alkyl, - (C 6 -C 20 ) -aryl-CONH- (C 1 -C 12 ) -alkyl, - (C 6 -C 20 ) -aryl-CON [(C 1 - C 12 ) alkyl] 2 , - (C 4 -C 20 ) heteroaryl, - (C 4 -C 20 ) heteroaryl (C 1 -C 12 ) alkyl, - (C 5 -C 8 ) cycloalkyl , - (C 6 -C 20 ) -aryl-CO- (C 6 -C 20 ) -aryl,
Z is selected from:
  • - (C 1 -C 12 ) -alkyl, - (C 6 -C 20 ) -aryl, - (C 6 -C 20 ) -aryl (C 1 -C 12 ) -alkyl, - (C 1 -C 12 ) alkyl (C 6 -C 20 ) arryh (C 4 -C 20 ) heteroaryl, (C 6 -C 20 ) aryl-CO- (C 6 -C 20 ) aryl -, - (C 6 -C 20 ) -aryl (C 6 -C 20 ) -aryl;
wherein said alkyl, heteroalkyl, cycloalkyl, heterocycloalkyl, aryl and heteroaryl groups may be substituted.
(C 1 -C 12 ) -alkyl and O- (C 1 -C 12 ) -alkyl can each be unsubstituted or substituted by one or more identical or different radicals selected from (C 3 -C 12 ) -cycloalkyl, (C 3 -C 12 ) -heterocycloalkyl, (C 6 -C 20 ) -aryl, fluorine, chlorine, cyano, formyl, acyl or alkoxycarbonyl.
(C 3 -C 12 ) -cycloalkyl and (C 3 -C 12 ) -heterocycloalkyl may each be unsubstituted or substituted by one or more identical or different radicals selected from (C 1 -C 12 ) -alkyl, (C 1 -C 12 ) -alkoxy, (C 3 -C 12 ) -cycloalkyl, (C 3 -C 12 ) -heterocycloalkyl, (C 6 -C 20 ) -aryl, fluorine, chlorine, cyano, formyl, acyl or alkoxycarbonyl.
(C 6 -C 20 ) -Aryl and - (C 6 -C 20 ) -aryl (C 6 -C 20 ) -aryl can each be unsubstituted or substituted by one or more identical or different radicals which are selected from -H, - (C 1 -C 12 ) -alkyl, -O- (C 1 -C 12 ) -alkyl, -O- (C 6 -C 20 ) -aryl, - (C 6 -C 20 ) -aryl , Halo (such as Cl, F, Br, I), -COO- (C 1 -C 12 ) alkyl, -CONH- (C 1 -C 12 ) alkyl, - (C 6 -C 20 ) aryl -CON [(C 1 -C 12 ) alkyl] 2 , -CO- (C 1 -C 12 ) alkyl, -CO- (C 6 -C 20 ) aryl, -COOH, -OH, -SO 3 H; -SO 3 Na, -NO 2 , -CN, -NH 2 , -N [(C 1 -C 12 ) -alkyl] 2 .

Im Rahmen der Erfindung umfasst der Ausdruck -(C1-C12)-Alkyl geradkettige und verzweigte Alkylgruppen. Vorzugsweise handelt es sich dabei um unsubstituierte geradkettige oder verzweigte -(C1-C8)-Alkyl- und ganz bevorzugt -(C1-C6)-Alkylgruppen. Beispiele für -(C1-C12)-Alkylgruppen sind insbesondere Methyl, Ethyl, Propyl, Isopropyl, n-Butyl, ido-Butyl, sec.-Butyl, tert.-Butyl, n-Pentyl, 2-Pentyl, 2-Methylbutyl-, 3-Methylbutyl-, 1,2-Dimethylpropyl-, 1,1-Dimethylpropyl, 2,2-Dimethylpropyl-, 1-Ethylpropyl-, n-Hexyl-, 2-Hexyl-, 2-Methylpentyl-, 3-Methylpentyl-, 4-Methylpentyl-, 1,1-Dimethylbutyl-, 1,2-Diemthylbutyl-, 2,2-Dimethylbutyl-, 1,3-Dimethylbutyl-, 2,3-Dimethylbutyl-, 3,3-Dimethylbutyl-, 1,1,2-Trimethylpropyl-, 1,2,2-Trimethylpropyl-, 1-Ethylbutyl-, 1-Ethyl-2-methylpropyl-, n-Heptyl-, 2-Heptyl-, 3-Heptyl-, 2-Ethylpentyl-, 1-Propylbutyl-, n-Octyl-, 2-Ethylhexyl-, 2-Propylheptyl-, Nonyl-, Decyl.In the context of the invention, the term - (C 1 -C 12 ) -alkyl comprises straight-chain and branched alkyl groups. Preferably, these are unsubstituted straight-chain or branched - (C 1 -C 8 ) -alkyl and most preferably - (C 1 -C 6 ) -alkyl groups. Examples of - (C 1 -C 12 ) -alkyl groups are, in particular, methyl, ethyl, propyl, isopropyl, n-butyl, ido-butyl, sec-butyl, tert-butyl, n-pentyl, 2-pentyl, 2- Methylbutyl, 3-methylbutyl, 1,2-dimethylpropyl, 1,1-dimethylpropyl, 2,2-dimethylpropyl, 1-ethylpropyl, n-hexyl, 2-hexyl, 2-methylpentyl, 3 Methylpentyl, 4-methylpentyl, 1,1-dimethylbutyl, 1,2-dimethylbutyl, 2,2-dimethylbutyl, 1,3-dimethylbutyl, 2,3-dimethylbutyl, 3,3-dimethylbutyl, 1,1,2-trimethylpropyl, 1,2,2-trimethylpropyl, 1-ethylbutyl, 1-ethyl-2-methylpropyl, n-heptyl, 2-heptyl, 3-heptyl, 2-ethylpentyl -, 1-Propylbutyl, n-octyl, 2-ethylhexyl, 2-propylheptyl, nonyl, decyl.

Die Erläuterungen zum Ausdruck -(C1-C12)-Alkyl gelten auch für die Alkylgruppen in -O-(C1-C12)-Alkyl, also in -(C1-C12)-Alkoxy. Vorzugsweise handelt es sich dabei um unsubstituierte geradkettige oder verzweigte -(C1-C6)-Alkoxygruppen.The explanations concerning the expression - (C 1 -C 12 ) -alkyl also apply to the alkyl groups in -O- (C 1 -C 12 ) -alkyl, ie in - (C 1 -C 12 ) -alkoxy. These are preferably unsubstituted straight-chain or branched - (C 1 -C 6 ) -alkoxy groups.

Substituierte -(C1-C12)-Alkylgruppen und substituierte -(C1-C12)-Alkoxygruppen können in Abhängigkeit von ihrer Kettenlänge, einen oder mehrere Substituenten aufweisen. Die Substituenten sind vorzugsweise unabhängig voneinander ausgewählt unter -(C3-C,2)-Cycloalkyl, -(C3-C12)-Heterocycloalkyl, -(C6-C20)-Aryl, Fluor, Chlor, Cyano, Formyl, Acyl oder Alkoxycarbonyl,Substituted - (C 1 -C 12 ) -alkyl groups and substituted - (C 1 -C 12 ) -alkoxy groups may, depending on their chain length, have one or more substituents. The substituents are preferably selected independently of one another from - (C 3 -C, 2 ) -cycloalkyl, (C 3 -C 12 ) -heterocycloalkyl, - (C 6 -C 20 ) -aryl, fluorine, chlorine, cyano, formyl, acyl or alkoxycarbonyl,

Der Ausdruck -(C3-C12)-Cycloalkyl umfasst im Sinne der vorliegenden Erfindung mono-, bi- oder tricyclische Kohlenwasserstoffreste mit 3 bis 12, insbesondere 5 bis 12 Kohlenstoffatomen. Dazu zählen Cyclopropyl-, Cyclobutyl-, Cyclopentyl-, Cyclohexyl-, Cycloheptyl-, Cyclooctyl-, Cyclododecyl-, Cyclopentadecyl-, Norbonyl- oder Adamantyl.For the purposes of the present invention, the term - (C 3 -C 12 ) -cycloalkyl encompasses mono-, bi- or tricyclic hydrocarbon radicals having 3 to 12, in particular 5 to 12, carbon atoms. These include cyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl, cycloheptyl, cyclooctyl, cyclododecyl, cyclopentadecyl, norbonyl or adamantyl.

Der Ausdruck -(C3-C12)-Heterocycloalkylgruppen umfasst im Sinne der vorliegenden Erfindung nichtaromatische, gesättigte oder teilweise ungesättigte cycloaliphatische Gruppen mit 3 bis 12, insbesondere 5 bis 12, Kohlenstoffatomen. Die -(C3-C12)-Heterocycloalkylgruppen weisen vorzugsweise 3 bis 8, besonders bevorzugt 5 oder 6, Ringatome auf. In den Heterocycloalkylgruppen sind im Unterschied zu den Cycloalkylgruppen 1,2,3 oder 4 der Ringkohlenstoffatome durch Heteroatome oder heteroatomhaltige Gruppen ersetzt. Die Heteroatome oder die heteroatomhaltige Gruppen sind vorzugsweise ausgewählt unter -O-, -S-, -N-, -N(=O)-, -C(=O)- oder -S(=O)-. Beispiele für -(C3-C12)-Heterocycloalkylgruppen Tetrahydrothiophenyl, Tetrhydrofuryl, Tetrahydropyranyl und Dioxanyl.The term - (C 3 -C 12 ) -heterocycloalkyl groups for the purposes of the present invention comprises non-aromatic, saturated or partially unsaturated cycloaliphatic groups having 3 to 12, in particular 5 to 12, carbon atoms. The - (C 3 -C 12 ) -heterocycloalkyl groups preferably have 3 to 8, more preferably 5 or 6, ring atoms. In the heterocycloalkyl groups, in contrast to the cycloalkyl groups 1, 2, 3 or 4, the ring carbon atoms are replaced by heteroatoms or heteroatom-containing groups. The heteroatoms or the heteroatom-containing groups are preferably selected from -O-, -S-, -N-, -N (= O) -, -C (= O) - or -S (= O) -. Examples of - (C 3 -C 12 ) -heterocycloalkyl groups include tetrahydrothiophenyl, tetrhydrofuryl, tetrahydropyranyl and dioxanyl.

Substituierte -(C3-C12)-Cycloalkylgruppen und substituierte -(C3-C12)-Heterocycloalkylgruppen können, in Abhängigkeit von ihrer Ringgröße, einen oder mehrere (z.B. 1, 2, 3, 4 oder 5) weitere Substituenten aufweisen. Diese Substituenten sind vorzugsweise unabhängig voneinander ausgewählt unter -(C1-C12)-Alkyl, -(C1-C12)-Alkoxy, -(C3-C12)-Cycloalkyl, -(C3-C12)-Heterocycloalkyl, -(C6-C20)-Aryl, Fluor, Chlor, Cyano, Formyl, Acyl oder Alkoxycarbonyl. Substituierte -(C3-C12)-Cycloalkylgruppen tragen vorzugsweise eine oder mehrere -(C1-C6)-Alkylgruppen. Substituierte -(C3-C12)-Heterocycloalkylgruppen tragen vorzugsweise eine oder mehrere -(C1-C6)-Alkylgruppen.Substituted - (C 3 -C 12 ) -cycloalkyl groups and substituted - (C 3 -C 12 ) -heterocycloalkyl groups may, depending on their ring size, have one or more (eg 1, 2, 3, 4 or 5) further substituents. These substituents are preferably independently selected from - (C 1 -C 12 ) -alkyl, - (C 1 -C 12 ) -alkoxy, - (C 3 -C 12 ) -cycloalkyl, - (C 3 -C 12 ) - Heterocycloalkyl, - (C 6 -C 20 ) -aryl, fluorine, chlorine, cyano, formyl, acyl or alkoxycarbonyl. Substituted - (C 3 -C 12 ) -cycloalkyl groups preferably carry one or more - (C 1 -C 6 ) -alkyl groups. Substituted - (C 3 -C 12 ) -heterocycloalkyl groups preferably carry one or more - (C 1 -C 6 ) -alkyl groups.

Der Ausdruck -(C6-C20)-Aryl und -(C6-C20)-Aryl-(C6-C20)-Aryl- umfasst im Sinne der vorliegenden Erfindung mono- oder polycyclische aromatische Kohlenwasserstoffreste. Diese weisen 6 bis 20 Ringatome, besonders bevorzugt 6 bis 14 Ringatome, insbesondere 6 bis 10 Ringatome, auf. Aryl steht vorzugsweise für -(C6-C10)-Aryl und -(C6-C10)-Aryl-(C6-C10)-Aryl-. Aryl steht insbesondere für Phenyl, Naphthyl, Indenyl, Fluorenyl, Anthracenyl, Phenanthrenyl, Naphthacenyl, Chrysenyl, Pyrenyl, Coronenyl. Insbesondere steht Aryl für Phenyl, Naphthyl und Antracenyl.The term - (C 6 -C 20 ) -aryl and - (C 6 -C 20 ) -aryl (C 6 -C 20 ) -aryl encompasses in the context of the present invention mono- or polycyclic aromatic hydrocarbon radicals. These have 6 to 20 ring atoms, particularly preferably 6 to 14 ring atoms, in particular 6 to 10 ring atoms, on. Aryl is preferably - (C 6 -C 10 ) -aryl and - (C 6 -C 10 ) -aryl (C 6 -C 10 ) -aryl. Aryl is especially phenyl, naphthyl, indenyl, fluorenyl, anthracenyl, phenanthrenyl, naphthacenyl, chrysenyl, pyrenyl, coronenyl. In particular, aryl is phenyl, naphthyl and antracenyl.

Substituierte -(C6-C20)-Arylgruppen und -(C6-C20)-Aryl-(C6-C20)-Arylgruppen können, in Abhängigkeit von der Ringgröße, einen oder mehrere (z.B. 1, 2, 3, 4 oder 5) Substituenten aufweisen. Diese Substituenten sind vorzugsweise unabhängig voneinander ausgewählt unter - H, -(C1-C12)-Alkyl, -O-(C1-C12)-Alkyl, -O-(C6-C20)-Aryl, -(C6-C20)-Aryl, -Halogen (wie Cl, F, Br, I),-COO-(C1-C12)-Alkyl, -CONH-(C1-C12)-Alkyl, -(C6-C20)-Aryl-CON[(C1-C12)-Alkyl]2, -CO-(C1-C12)-Alkyl, -CO-(C6-C20)-Aryl, -COOH, -OH, -SO3H; -SO3Na, -NO2, -CN, -NH2, -N[(C1-C12)-Alkyl]2.Substituted - (C 6 -C 20 ) -aryl groups and - (C 6 -C 20 ) -aryl (C 6 -C 20 ) -aryl groups can, depending on the ring size, one or more (eg 1, 2, 3 , 4 or 5) have substituents. These substituents are preferably independently selected from --H, - (C 1 -C 12 ) -alkyl, -O- (C 1 -C 12 ) -alkyl, -O- (C 6 -C 20 ) -aryl, - ( C 6 -C 20 ) -aryl, -halogen (such as Cl, F, Br, I), -COO- (C 1 -C 12 ) -alkyl, -CONH- (C 1 -C 12 ) -alkyl, - ( C 6 -C 20 ) -aryl-CON [(C 1 -C 12 ) -alkyl] 2 , -CO- (C 1 -C 12 ) -alkyl, -CO- (C 6 -C 20 ) -aryl, COOH, -OH, -SO 3 H; -SO 3 Na, -NO 2 , -CN, -NH 2 , -N [(C 1 -C 12 ) -alkyl] 2 .

Substituierte -(C6-C20)-Arylgruppen und -(C6-C20)-Aryl-(C6-C20)-Arylgruppen sind vorzugsweise substituierte -(C6-C10)-Arylgruppen und -(C6-C10)-Aryl-(C6-C10)-Arylgruppen, insbesondere substituiertes Phenyl oder substituiertes Naphthyl oder substituiertes Anthracenyl. Substituierte -(C6-C20)-Arylgruppen tragen vorzugsweise eine oder mehrere z.B. 1, 2, 3, 4 oder 5 Substituenten, ausgewählt unter -(C1-C12)-Alkylgruppen, -(C1-C12)-Alkoxygruppen.Substituted - (C 6 -C 20 ) -aryl groups and - (C 6 -C 20 ) -aryl (C 6 -C 20 ) -aryl groups are preferably substituted - (C 6 -C 10 ) -aryl groups and - (C 6 -C 10 ) aryl- (C 6 -C 10 ) -aryl groups, in particular substituted phenyl or substituted naphthyl or substituted anthracenyl. Substituted - (C 6 -C 20 ) -aryl groups preferably carry one or more, for example 1, 2, 3, 4 or 5 substituents selected from - (C 1 -C 12 ) -alkyl groups, - (C 1 -C 12 ) - alkoxy groups.

In einer Ausführungsform sind X und Y jeweils unabhängig voneinander ausgewählt aus:

  • -(C1-C12)-Alkyl, -(C6-C20)-Aryl, -(C6-C20)-Aryl-(C1-C12)-Alkyl, -(C6-C20)-Aryl-O-(C1-C12)-Alkyl, -(C6-C20)-Aryl-COO-(C1-C12)-Alkyl, -(C6-C20)-Aryl-CONH-(C1-C12)-Alkyl, -(C6-C20)-Aryl-CON[(C1-C12)-Alkyl]2, -(C4-C20)-Heteroaryl, -(C4-C20)-Heteroaryl-(C1-C12)-Alkyl.
In one embodiment, X and Y are each independently selected from:
  • - (C 1 -C 12 ) -alkyl, - (C 6 -C 20 ) -aryl, - (C 6 -C 20 ) -aryl (C 1 -C 12 ) -alkyl, - (C 6 -C 20 ) -Aryl-O- (C 1 -C 12 ) -alkyl, - (C 6 -C 20 ) -aryl-COO- (C 1 -C 12 ) -alkyl, - (C 6 -C 20 ) -aryl- CONH (C 1 -C 12 ) -alkyl, - (C 6 -C 20 ) -aryl-CON [(C 1 -C 12 ) -alkyl] 2 , - (C 4 -C 20 ) -heteroaryl, - ( C 4 -C 20 ) heteroaryl (C 1 -C 12 ) alkyl.

In einer Ausführungsform sind X und Y jeweils unabhängig voneinander ausgewählt aus:

  • -(C1-C12)-Alkyl, -(C6-C20)-Aryl, -(C6-C20)-Aryl-(C1-C12)-Alkyl, -(C6-C20)-Aryl-O-(C1-C12)-Alkyl, -(C6-C20)-Aryl-COO-(C1-C12)-Alkyl.
In one embodiment, X and Y are each independently selected from:
  • - (C 1 -C 12 ) -alkyl, - (C 6 -C 20 ) -aryl, - (C 6 -C 20 ) -aryl (C 1 -C 12 ) -alkyl, - (C 6 -C 20 ) -Aryl-O- (C 1 -C 12 ) -alkyl, - (C 6 -C 20 ) -aryl-COO- (C 1 -C 12 ) -alkyl.

In einer Ausführungsform sind X und Y jeweils unabhängig voneinander ausgewählt aus:

  • -(C1-C12)-Alkyl, -(C6-C20)-Aryl, -(C6-C20)-Aryl-(C1-C12)-Alkyl, -(C6-C20)-Aryl-O-(C1-C12)-Alkyl.
In one embodiment, X and Y are each independently selected from:
  • - (C 1 -C 12 ) -alkyl, - (C 6 -C 20 ) -aryl, - (C 6 -C 20 ) -aryl (C 1 -C 12 ) -alkyl, - (C 6 -C 20 ) -Aryl-O- (C 1 -C 12 ) -alkyl.

In einer Ausführungsform ist Z ausgewählt aus:

  • -(C1-C12)-Alkyl-, -(C6-C20)-Aryl-, -(C6-C20)-Aryl-(C1-C12)-Alkyl-, -(C6-C20)-Aryl-CO-(C6-C20)-Aryl-,-(C1-C12)-Alkyl-(C6-C20)-Aryl-, -(C6-C20)-Aryl-(C6-C20)-Aryl-.
In one embodiment, Z is selected from:
  • - (C 1 -C 12 ) -alkyl, - (C 6 -C 20 ) -aryl, - (C 6 -C 20 ) -aryl (C 1 -C 12 ) -alkyl, - (C 6 -C 20 ) aryl-CO- (C 6 -C 20 ) -aryl, - (C 1 -C 12 ) -alkyl- (C 6 -C 20 ) -aryl, - (C 6 -C 20 ) -Aryl- (C 6 -C 20 ) -Aryl-.

In einer Ausführungsform steht Z für:

Figure imgb0003
In one embodiment, Z stands for:
Figure imgb0003

In einer Ausführungsform steht Z für:

  • -(C6-C20)-Aryl-(C6-C20)-Aryl-.
In one embodiment, Z stands for:
  • - (C 6 -C 20 ) -aryl (C 6 -C 20 ) -aryl.

In einer Ausführungsform sind R1, R2, R3, R4, R5, R6, R7, R8 jeweils unabhängig voneinander ausgewählt aus:

  • -H, -(C1-C12)-Alkyl, -O-(C1-C12)-Alkyl, -O-(C6-C20)-Aryl, -(C6-C20)-Aryl, -COO-(C1-C12)-Alkyl, - CONH-(C1-C12)-Alkyl, -(C6-C20)-Aryl-CON[(C1-C12)-Alkyl]2, -CO-(C1-C12)-Alkyl, -CO-(C6-C20)-Aryl, -COOH, -OH, -NH2, -N[(C1-C12)-Alkyl]2.
In one embodiment, R 1 , R 2 , R 3 , R 4 , R 5 , R 6 , R 7 , R 8 are each independently selected from:
  • -H, - (C 1 -C 12 ) -alkyl, -O- (C 1 -C 12 ) -alkyl, -O- (C 6 -C 20 ) -aryl, - (C 6 -C 20 ) -aryl , -COO- (C 1 -C 12 ) -alkyl, - CONH- (C 1 -C 12 ) -alkyl, - (C 6 -C 20 ) -aryl-CON [(C 1 -C 12 ) -alkyl] 2 , -CO- (C 1 -C 12 ) -alkyl, -CO- (C 6 -C 20 ) -aryl, -COOH, -OH, -NH 2 , -N [(C 1 -C 12 ) -alkyl ] 2 .

In einer Ausführungsform sind R1, R2, R3, R4, R5, R6, R7, R8 jeweils unabhängig voneinander ausgewählt aus:

  • -H, -(C1-C12)-Alkyl, -O-(C1-C12)-Alkyl, -O-(C6-C20)-Aryl, -(C6-C20)-Aryl, -COO-(C1-C12)-Alkyl, - N[(C1-C12)-Alkyl]2.
In one embodiment, R 1 , R 2 , R 3 , R 4 , R 5 , R 6 , R 7 , R 8 are each independently selected from:
  • -H, - (C 1 -C 12 ) -alkyl, -O- (C 1 -C 12 ) -alkyl, -O- (C 6 -C 20 ) -aryl, - (C 6 -C 20 ) -aryl , -COO- (C 1 -C 12 ) -alkyl, - N [(C 1 -C 12 ) -alkyl] 2 .

In einer Ausführungsform sind R1, R2, R3, R4, R5, R6, R7, R8 jeweils unabhängig voneinander ausgewählt aus:

  • -H, -(C1-C12)-Alkyl, -O-(C1-C12)-Alkyl, -(C6-C20)-Aryl.
In one embodiment, R 1 , R 2 , R 3 , R 4 , R 5 , R 6 , R 7 , R 8 are each independently selected from:
  • -H, - (C 1 -C 12 ) -alkyl, -O- (C 1 -C 12 ) -alkyl, - (C 6 -C 20 ) -aryl.

In einer Ausführungsform stehen X und Y für die gleichen Reste.In one embodiment, X and Y are the same radicals.

In einer Ausführungsform stehen R3 und R6 für -O-(C1-C12)-Alkyl.In one embodiment, R 3 and R 6 are -O- (C 1 -C 12 ) -alkyl.

In einer Ausführungsform stehen R3 und R6 für -OMe.In one embodiment, R 3 and R 6 are -OMe.

In einer Ausführungsform stehen R1 und R8 für -(C1-C12)-Alkyl.In one embodiment, R 1 and R 8 are - (C 1 -C 12 ) alkyl.

In einer Ausführungsform stehen R1 und R8 für tert-Butyl.In one embodiment, R 1 and R 8 are tert -butyl.

In einer Ausführungsform stehen R1, R3, R6 und R8 für -(C1-C12)-Alkyl.In one embodiment, R 1 , R 3 , R 6 and R 8 are - (C 1 -C 12 ) -alkyl.

In einer Ausführungsform stehen R1, R 3 R6 und R8 für Methyl.In one embodiment, R 1 , R 3, R 6 and R 8 are methyl.

In einer Ausführungsform stehen R1, R 3 R6 und R8 für tert-Butyl.In one embodiment, R 1 , R 3, R 6 and R 8 are tert -butyl.

In einer Ausführungsform stehen sind R1, R2, R3, R4, R5, R6, R7 und R8 für -H.In one embodiment, R 1 , R 2 , R 3 , R 4 , R 5 , R 6 , R 7 and R 8 are -H.

In einer Ausführungsform weist der Ligand die allgemeine Strukturen III auf:

Figure imgb0004
wobei R9, R10, R11, R12, R13, R14, R15, R16 jeweils unabhängig voneinander ausgewählt sind aus:

  • -H, -(C1-C12)-Alkyl, -O-(C1-C12)-Alkyl, -O-(C6-C20)-Aryl, -(C6-C20)-Aryl, -Halogen (wie Cl, F, Br, I), -COO-(C1-C12)-Alkyl, -CONH-(C1-C12)-Alkyl, -(C6-C20)-Aryl-CON[(C1-C12)-Alkyl]2, -CO-(C1-C12)-Alkyl, -CO-(C6-C20)-Aryl, -COOH, -OH, -SO3H, -SO3Na, -NO2, -CN, -NH2, -N[(C1-C12)-Alkyl]2.
In one embodiment, the ligand has the general structures III :
Figure imgb0004
 wherein R 9 , R 10 , R 11 , R 12 , R 13 , R 14 , R 15 , R 16 are each independently selected from:
  • -H, - (C 1 -C 12 ) -alkyl, -O- (C 1 -C 12 ) -alkyl, -O- (C 6 -C 20 ) -aryl, - (C 6 -C 20 ) -aryl , Halo (such as Cl, F, Br, I), -COO- (C 1 -C 12 ) alkyl, -CONH- (C 1 -C 12 ) alkyl, - (C 6 -C 20 ) aryl -CON [(C 1 -C 12 ) alkyl] 2 , -CO- (C 1 -C 12 ) alkyl, -CO- (C 6 -C 20 ) aryl, -COOH, -OH, -SO 3 H, -SO 3 Na, -NO 2 , -CN, -NH 2 , -N [(C 1 -C 12 ) -alkyl] 2 .

In einer Ausführungsform sind R9, R10, R11, R12, R13, R14, R15, R16 jeweils unabhängig voneinander ausgewählt aus:

  • -H, -(C1-C12)-Alkyl, -O-(C1-C12)-Alkyl, -O-(C6-C20)-Aryl, -(C6-C20)-Aryl, -COO-(C1-C12)-Alkyl, - CONH-(C1-C12)-Alkyl, -(C6-C20)-Aryl-CON[(C1-C12)-Alkyl]2, -CO-(C1-C12)-Alkyl, -CO-(C6-C20)-Aryl,-COOH, -OH, -NH2, -N[(C1-C12)-Alkyl]2.
In one embodiment, R 9 , R 10 , R 11 , R 12 , R 13 , R 14 , R 15 , R 16 are each independently selected from:
  • -H, - (C 1 -C 12 ) -alkyl, -O- (C 1 -C 12 ) -alkyl, -O- (C 6 -C 20 ) -aryl, - (C 6 -C 20 ) -aryl , -COO- (C 1 -C 12 ) -alkyl, - CONH- (C 1 -C 12 ) -alkyl, - (C 6 -C 20 ) -aryl-CON [(C 1 -C 12 ) -alkyl] 2 , -CO- (C 1 -C 12 ) -alkyl, -CO- (C 6 -C 20 ) -aryl, -COOH, -OH, -NH 2 , -N [(C 1 -C 12 ) -alkyl ] 2 .

In einer Ausführungsform sind R9, R10, R11, R12, R13, R14, R15, R16 jeweils unabhängig voneinander ausgewählt aus:

  • -H, -(C1-C12)-Alkyl, -O-(C1-C12)-Alkyl, -O-(C6-C20)-Aryl, -(C6-C20)-Aryl, -COO-(C1-C12)-Alkyl, - N[(C1-C12)-Alkyl]2.
In one embodiment, R 9 , R 10 , R 11 , R 12 , R 13 , R 14 , R 15 , R 16 are each independently selected from:
  • -H, - (C 1 -C 12 ) -alkyl, -O- (C 1 -C 12 ) -alkyl, -O- (C 6 -C 20 ) -aryl, - (C 6 -C 20 ) -aryl , -COO- (C 1 -C 12 ) -alkyl, - N [(C 1 -C 12 ) -alkyl] 2 .

In einer Ausführungsform sind R9, R10, R11, R12, R13, R14, R15, R16 jeweils unabhängig voneinander ausgewählt aus:

  • -H, -(C1-C12)-Alkyl, -O-(C1-C12)-Alkyl, -(C6-C20)-Aryl
wobei Alkyl 1-12 Kohlenstoffatome, bevorzugt 1-10 Kohlenstoffatome z.B. primäre, sekundäre oder tertiäre Alkylgruppen, wie Methyl-, Ethyl-, n-Propyl-, Isopropyl-, Butyl-, sec-Butyl-, t-Butyl-, t-Butylethyl-, t-Butylpropyl-, n-Hexyl-, Amyl-, sec-Amyl-, t-Amyl-, iso-Octyl-, 2-Ethylhexyl-, Decyl-, Dodecyl- und Octadecylgruppen umfasst.In one embodiment, R 9 , R 10 , R 11 , R 12 , R 13 , R 14 , R 15 , R 16 are each independently selected from:
  • -H, - (C 1 -C 12 ) -alkyl, -O- (C 1 -C 12 ) -alkyl, - (C 6 -C 20 ) -aryl
where alkyl is 1-12 carbon atoms, preferably 1-10 carbon atoms, for example primary, secondary or tertiary alkyl groups, such as methyl, ethyl, n-propyl, isopropyl, butyl, sec-butyl, t-butyl, t Butylethyl, t-butylpropyl, n-hexyl, amyl, sec-amyl, t-amyl, isooctyl, 2-ethylhexyl, decyl, dodecyl and octadecyl groups.

In einer Ausführungsform stehen R11 und R14 für -O-(C1-C12)-Alkyl.In one embodiment, R 11 and R 14 are -O- (C 1 -C 12 ) -alkyl.

In einer Ausführungsform stehen R11 und R14 für -OMe.In one embodiment, R 11 and R 14 are -OMe.

In einer Ausführungsform stehen R9 und R16 für -(C1-C12)-Alkyl.In one embodiment, R 9 and R 16 are - (C 1 -C 12 ) alkyl.

In einer Ausführungsform stehen R9 und R16 für tert-Butyl.In one embodiment, R 9 and R 16 are tert -butyl.

In einer Ausführungsform stehen R9, R11, R14 und R16 für -(C1-C12)-Alkyl.In one embodiment, R 9 , R 11 , R 14 and R 16 are - (C 1 -C 12 ) -alkyl.

In einer Ausführungsform stehen R9, R11, R14 und R16 für Methyl.In one embodiment, R 9 , R 11 , R 14 and R 16 are methyl.

In einer Ausführungsform stehen R9, R11, R14 und R16 für tert-Butyl.In one embodiment, R 9 , R 11 , R 14 and R 16 are tert -butyl.

In einer Ausführungsform stehen sind R9, R10, R11, R12, R13, R14, R15 und R16 für -H.In one embodiment, R 9 , R 10 , R 11 , R 12 , R 13 , R 14 , R 15 and R 16 are -H.

In einer Ausführungsform weist der Ligand die allgemeine Strukturen IV auf:

Figure imgb0005
wobei R9, R10, R11, R12, R13 , R14 , R15 R16 jeweils unabhängig voneinander ausgewählt sind aus:

  • -H, -(C1-C12)-Alkyl, -O-(C1-C12)-Alkyl, -O-(C6-C20)-Aryl, -(C6-C20)-Aryl, -Halogen (wie Cl, F, Br, I), -COO-(C1-C12)-Alkyl, -CONH-(C1-C12)-Alkyl, -(C6-C20)-Aryl-CON[(C1-C12)-Alkyl]2, -CO-(C1-C12)-Alkyl, -CO-(C6-C20)-Aryl, -COOH, -OH, -SO3H, -SO3Na, -NO2, -CN, -NH2, -N[(C1-C12)-Alkyl]2.
In one embodiment, the ligand has the general structures IV :
Figure imgb0005
 wherein R 9 , R 10 , R 11 , R 12 , R 13 , R 14 , R 15 R 16 are each independently selected from:
  • -H, - (C 1 -C 12 ) -alkyl, -O- (C 1 -C 12 ) -alkyl, -O- (C 6 -C 20 ) -aryl, - (C 6 -C 20 ) -aryl , Halo (such as Cl, F, Br, I), -COO- (C 1 -C 12 ) alkyl, -CONH- (C 1 -C 12 ) alkyl, - (C 6 -C 20 ) aryl -CON [(C 1 -C 12 ) alkyl] 2 , -CO- (C 1 -C 12 ) alkyl, -CO- (C 6 -C 20 ) aryl, -COOH, -OH, -SO 3 H, -SO 3 Na, -NO 2 , -CN, -NH 2 , -N [(C 1 -C 12 ) -alkyl] 2 .

In einer Ausführungsform sind R9, R10, R11, R12, R13, R14, R15, R16 jeweils unabhängig voneinander ausgewählt aus:

  • -H, -(C1-C12)-Alkyl, -O-(C1-C12)-Alkyl, -O-(C6-C20)-Aryl, -(C6-C20)-Aryl, -COO-(C1-C12)-Alkyl, - CONH-(C1-C12)-Alkyl, -(C6-C20)-Aryl-CON[(C1-C12)-Alkyl]2, -CO-(C1-C12)-Alkyl, -CO-(C6-C20)-Aryl,-COOH, -OH, -NH2; -N[(C1-C12)-Alkyl]2.
In one embodiment, R 9 , R 10 , R 11 , R 12 , R 13 , R 14 , R 15 , R 16 are each independently selected from:
  • -H, - (C 1 -C 12 ) -alkyl, -O- (C 1 -C 12 ) -alkyl, -O- (C 6 -C 20 ) -aryl, - (C 6 -C 20 ) -aryl , -COO- (C 1 -C 12 ) -alkyl, - CONH- (C 1 -C 12 ) -alkyl, - (C 6 -C 20 ) -aryl-CON [(C 1 -C 12 ) -alkyl] 2 , -CO- (C 1 -C 12 ) -alkyl, -CO- (C 6 -C 20 ) -aryl, -COOH, -OH, -NH 2 ; -N [(C 1 -C 12 ) -alkyl] 2 .

In einer Ausführungsform sind R9, R10, R11, R12, R13, R14, R15, R16 jeweils unabhängig voneinander ausgewählt aus:

  • -H, -(C1-C12)-Alkyl, -O-(C1-C12)-Alkyl, -O-(C6-C20)-Aryl, -(C6-C20)-Aryl, -COO-(C1-C12)-Alkyl,-N[(C1-C12)-Alkyl]2.
In one embodiment, R 9 , R 10 , R 11 , R 12 , R 13 , R 14 , R 15 , R 16 are each independently selected from:
  • -H, - (C 1 -C 12 ) -alkyl, -O- (C 1 -C 12 ) -alkyl, -O- (C 6 -C 20 ) -aryl, - (C 6 -C 20 ) -aryl , -COO- (C 1 -C 12 ) -alkyl, -N [(C 1 -C 12 ) -alkyl] 2 .

In einer Ausführungsform sind R9, R10, R11, R12, R13, R14, R15, R16 jeweils unabhängig voneinander ausgewählt aus:

  • -H, -(C1-C12)-Alkyl, -O-(C1-C12)-Alkyl, -(C6-C20)-Aryl;
wobei Alkyl 1-18 Kohlenstoffatome, bevorzugt 1-10 Kohlenstoffatome z.B. primäre, sekundäre oder tertiäre Alkylgruppen, wie Methyl-, Ethyl-, n-Propyl-, Isopropyl-, Butyl-, sec-Butyl-, t-Butyl-, t-Butylethyl-, t-Butylpropyl-, n-Hexyl-, Amyl-, sec-Amyl-, t-Amyl-, iso-Octyl-, 2-Ethylhexyl-, Decyl-, Dodecyl- und Octadecylgruppen umfasst.In one embodiment, R 9 , R 10 , R 11 , R 12 , R 13 , R 14 , R 15 , R 16 are each independently selected from:
  • -H, - (C 1 -C 12 ) -alkyl, -O- (C 1 -C 12 ) -alkyl, - (C 6 -C 20 ) -aryl;
where alkyl is 1-18 carbon atoms, preferably 1-10 carbon atoms, for example primary, secondary or tertiary alkyl groups, such as methyl, ethyl, n-propyl, isopropyl, butyl, sec-butyl, t-butyl, t Butylethyl, t-butylpropyl, n-hexyl, amyl, sec-amyl, t-amyl, isooctyl, 2-ethylhexyl, decyl, dodecyl and octadecyl groups.

In einer Ausführungsform stehen R11 und R14 für -O-(C1-C12)-Alkyl.In one embodiment, R 11 and R 14 are -O- (C 1 -C 12 ) -alkyl.

In einer Ausführungsform stehen R11 und R14 für -OMe.In one embodiment, R 11 and R 14 are -OMe.

In einer Ausführungsform stehen R9 und R16 für -(C1-C12)-Alkyl.In one embodiment, R 9 and R 16 are - (C 1 -C 12 ) alkyl.

In einer Ausführungsform stehen R9 und R16 für tert-Butyl.In one embodiment, R 9 and R 16 are tert -butyl.

In einer Ausführungsform stehen R9, R11, R14 und R16 für -(C1-C12)-Alkyl.In one embodiment, R 9 , R 11 , R 14 and R 16 are - (C 1 -C 12 ) -alkyl.

In einer Ausführungsform stehen R9, R11, R14 und R16 für Methyl.In one embodiment, R 9 , R 11 , R 14 and R 16 are methyl.

In einer Ausführungsform stehen R9, R11, R14 und R16 für tert-Butyl.In one embodiment, R 9 , R 11 , R 14 and R 16 are tert -butyl.

In einer Ausführungsform stehen sind R9, R10, R11, R12, R13, R14, R15 und R16 für -H.In one embodiment, R 9 , R 10 , R 11 , R 12 , R 13 , R 14 , R 15 and R 16 are -H.

Neben den Liganden wird auch ein Komplex beansprucht, welcher diese Liganden umfasst.In addition to the ligands, a complex is claimed which comprises these ligands.

Komplex umfassend:

  • einen zuvor beschriebenen Liganden,
  • ein Metallatom ausgewählt aus: Rh, Ru, Co, Ir.
Complex comprising:
  • a previously described ligand,
  • a metal atom selected from: Rh, Ru, Co, Ir.

In einer bevorzugten Ausführungsform ist das Metall Rh.In a preferred embodiment, the metal is Rh.

Siehe hierzu R. Franke, D. Selent, A. Börner, "Applied Hydroformylation", Chem. Rev., 2012 , DOI:10.1021/cr3001803; S. 5688 Schema 12 "General Method for the Preparation of a P-Modified Rh precatalyst" und darin zitierte Literaturstellen sowie P. W. N. M. van Leeuwen, in Rhodium Catalyzed Hydroformylation, P. W. N. M. van Leeuwen, C. Claver (Hrsg.), Kluwer, Dordrecht, 2000 unter anderem S. 48 ff, S.233 ff. und darin zitierte Literaturstellen sowie K.D. Wiese und D. Obst in Top. Organomet. Chem. 2006, 18, 1-13; Springer Verlag Berlin Heidelberg 2006 S. 6 ff sowie darin zitierte Literaturstellen.See also R. Franke, D. Selent, A. Börner, Applied Hydroformylation, Chem. Rev., 2012 , DOI: 10.1021 / cr3001803; P. 5688 Scheme 12 "General Method for the Preparation of a P-Modified Rh precatalyst" and references cited therein as well PWNM van Leeuwen, in Rhodium Catalyzed Hydroformylation, PWNM van Leeuwen, C. Claver (ed.), Kluwer, Dordrecht, 2000 et al., P. 48 et seq., P.233 et seq. and references cited therein as well KD meadow and D. fruit in top. Organomet. Chem. 2006, 18, 1-13; Springer Verlag Berlin Heidelberg 2006 p. 6 ff and references cited therein.

Des Weiteren wird die Verwendung des Liganden als Ligand in einem Ligand-Metall-Komplex zur Katalyse einer Hydroformylierungsreaktion beansprucht.Furthermore, the use of the ligand as a ligand in a ligand-metal complex for catalysing a hydroformylation reaction is claimed.

Verwendung eines zuvor beschriebenen Liganden in einem Ligand-Metall-Komplex zur Katalyse einer Hydroformylierungsreaktion.Use of a previously described ligand in a ligand-metal complex to catalyze a hydroformylation reaction.

Das Verfahren bei dem der Ligand als Ligand in einem Ligand-Metall-Komplex zur Umsetzung eines Olefins zu einem Aldehyd eingesetzt wird, wird ebenfalls beansprucht.The process in which the ligand is used as a ligand in a ligand-metal complex to convert an olefin to an aldehyde is also claimed.

Verfahren umfassend die Verfahrensschritte:

  1. a) Vorlegen eines Olefins,
  2. b) Zugabe eines zuvor beschriebenen Komplexes,
    oder eines zuvor beschriebenen Liganden und einer Verbindung, welche ein Metallatom ausgewählt aus: Rh, Ru, Co, Ir aufweist,
  3. c) Zuführen von H2 und CO,
  4. d) Erwärmen des Reaktionsgemisches, wobei das Olefin zu einem Aldehyd umgesetzt wird.
Method comprising the method steps:
  1. a) presentation of an olefin,
  2. b) addition of a complex described above,
    or a ligand described above and a compound having a metal atom selected from: Rh, Ru, Co, Ir,
  3. c) supplying H 2 and CO,
  4. d) heating the reaction mixture, wherein the olefin is reacted to an aldehyde.

Hierbei können die Verfahrensschritte a) bis d) in beliebiger Reihenfolge erfolgen.Here, the process steps a) to d) can be carried out in any order.

Die Reaktion wird bei üblichen Bedingungen durchgeführt.The reaction is carried out under usual conditions.

Bevorzugt sind eine Temperatur von 80 °C bis 160 °C und ein Druck von 1 bis 300 bar.Preferred are a temperature of 80 ° C to 160 ° C and a pressure of 1 to 300 bar.

Besonders bevorzugt sind eine Temperatur von 100 °C bis 160 °C und ein Druck von 15 bis 250 bar.Particularly preferred are a temperature of 100 ° C to 160 ° C and a pressure of 15 to 250 bar.

In einer bevorzugten Ausführungsform ist das Metall Rh.In a preferred embodiment, the metal is Rh.

Die Edukte für die Hydroformylierung gemäß dem Verfahren der Erfindung sind Olefine oder Gemische von Olefinen, insbesondere Monoolefine mit 2 bis 24, bevorzugt 3 bis 16, besonders bevorzugt 3 bis 12 Kohlenstoffatomen mit end- oder innenständigen C-C-Doppelbindungen, wie z.B. 1-Propen, 1-Buten, 2-Buten, 1- oder 2-Penten, 2-Methyl-1-buten, 2-Methyl-2-buten, 3-Methyl-1-buten, 1-, 2- oder 3,-Hexen, das bei der Dimerisierung von Propen anfallende C6-Olefingemisch (Dipropen), Heptene, 2- oder 3-Methyl-1-hexene, Octene, 2-Methylheptene, 3-Methylheptene, 5-Methyl-2-hepten, 6-Methyl-2-hepten, 2-Ethyl-1-hexen, das bei der Dimerisierung von Butenen anfallende C8-Olefingemisch (Di-n-buten, Di-iso-buten), Nonene, 2-oder 3-Methyloctene, das bei der Trimerisierung von Propen anfallende C9-Olefingemisch (Tripropen), Decene, 2-Ethyl-1-octen, Dodecene, das bei der Tetramerisierung von Propen oder der Trimerisierung von Butenen anfallende C12-Olefingemisch (Tetrapropen oder Tributen), Tetradecene, Hexadecene, das bei der Tetramerisierung von Butenen anfallende C16-Olefingemisch (Tetrabuten) sowie durch Cooligomerisierung von Olefinen mit unterschiedlicher Anzahl von Kohlenstoffatomen (bevorzugt 2 bis 4) hergestellte Olefingemische.The educts for the hydroformylation according to the process of the invention are olefins or mixtures of olefins, in particular monoolefins having 2 to 24, preferably 3 to 16, particularly preferably 3 to 12 carbon atoms with terminal or internal CC double bonds, such as 1-propene, 1-butene, 2-butene, 1- or 2-pentene, 2-methyl-1-butene, 2-methyl-2-butene, 3-methyl-1-butene, 1, 2 or 3, -hexene, the C 6 olefin mixture (dipropene), heptene, 2- or 3-methyl-1-hexenes, octenes, 2-methylheptene, 3-methylheptene, 5-methyl-2-heptene, 6-methylene obtained in the dimerization of propene 2-heptene, 2-ethyl-1-hexene, the C 8 olefin mixture (di-n-butene, di-iso-butene), nonenes, 2- or 3-methyloctenes obtained in the dimerization of butenes, in the trimerization propene-derived C 9 olefin mixture (tripropene), decene, 2-ethyl-1-octene, dodecenes, the C 12 olefin mixture (tetrapropene or tributene) obtained in the tetramerization of propene or the trimerization of butenes, tetradecene ne, Hexadecene, the obtained in the tetramerization of butenes C 16 -Olefingemisch (tetrabutene) as well as by co-oligomerization of olefins with different numbers of carbon atoms (preferably 2 to 4) prepared olefin mixtures.

Mit dem erfindungsgemäßen Verfahren können unter Verwendung der erfindungsgemäßen Liganden α-Olefine, endständig verzweigte, innenständige und innenständig verzweigte Olefine hydroformyliert werden. Bemerkenswert ist dabei die hohe Ausbeute an endständig hydrofomyliertem Olefin, selbst wenn im Edukt nur ein geringer Anteil an Olefinen mit endständiger Doppelbindung vorhanden war.With the process according to the invention, α-olefins, terminally branched, internally branched and internally branched olefins can be hydroformylated using the ligands according to the invention. Noteworthy here is the high yield of terminally hydrofomylated olefin, even if only a small proportion of olefins with terminal double bond was present in the educt.

Im Folgenden soll die Erfindung anhand von Ausführungsbeispielen näher erläutert werden.In the following, the invention will be explained in more detail with reference to exemplary embodiments.

Die folgenden siebzig Strukturen (1 bis 70) zeigen mögliche Ausführungsbeispiele des Liganden:

Figure imgb0006
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Figure imgb0038
 The following seventy structures (1 to 70) show possible embodiments of the ligand:
Figure imgb0006
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Figure imgb0024
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Figure imgb0035
Figure imgb0036
Figure imgb0037
Figure imgb0038

Allgemeine ArbeitsvorschriftenGeneral working instructions

Alle nachfolgenden Präparationen wurden mit Standard-Schlenk-Technik unter Schutzgas durchgeführt. Die Lösungsmittel wurden vor Gebrauch über geeigneten Trocknungsmitteln getrocknet ( Purification of Laboratory Chemicals, W. L. F. Armarego, Christina Chai, Butterworth Heinemann (Elsevier), 6. Auflage, Oxford 2009 ).All subsequent preparations were performed with standard Schlenk technique under inert gas. The solvents were dried before use over suitable desiccants ( Purification of Laboratory Chemicals, WLF Armarego, Christina Chai, Butterworth Heinemann (Elsevier), 6th edition, Oxford 2009 ).

Alle präparativen Arbeiten erfolgten in ausgeheizten Gefäßen. Die Charakterisierung der Produkte erfolgte mittels NMR-Spektroskopie. Chemische Verschiebungen (δ) werden in ppm angegeben. Die Referenzierung der 31P-NMR-Signale erfolgte gemäß: SR31P = SR1H * (BF31P / BF1H) = SR1H * 0,4048. ( Robin K. Harris, Edwin D. Becker, Sonia M. Cabral de Menezes, Robin Goodfellow, and Pierre Granger, Pure Appl. Chem., 2001, 73, 1795-1818 ; Robin K. Harris, Edwin D. Becker, Sonia M. Cabral de Menezes, Pierre Granger, Roy E. Hoffman and Kurt W. Zilm, Pure Appl. Chem., 2008, 80, 59-84 ).All preparative work was done in baked-out vessels. The products were characterized by NMR spectroscopy. Chemical shifts (δ) are reported in ppm. Referencing of the 31 P NMR signals was according to: SR 31P = SR 1H * (BF 31P / BF 1H ) = SR 1H * 0.4048. ( Robin K. Harris, Edwin D. Becker, Sonia M. Cabral de Menezes, Robin Goodfellow, and Pierre Granger, Pure Appl. Chem., 2001, 73, 1795-1818 ; Robin K. Harris, Edwin D. Becker, Sonia M. Cabral de Menezes, Pierre Granger, Roy E. Hoffman and Kurt W. Zilm, Pure Appl. Chem., 2008, 80, 59-84 ).

Die Aufnahme von Kernresonanzspektren erfolgte mittels eines Bruker Avance 300 bzw. Bruker Avance 400, die gaschromatografische Analyse an Agilent GC 7890A.Nuclear resonance spectra were recorded using a Bruker Avance 300 and Bruker Avance 400, respectively, and gas chromatographic analysis on Agilent GC 7890A.

Die erfindungsgemäßen Liganden lassen sich hierbei auf verschiedenen Wegen herstellen. Drei mögliche Wege sind in den nachfolgenden Schemata (A bis C) dargestellt.The ligands according to the invention can be prepared in various ways. Three possible ways are shown in the following schemes (A to C).

Die dargestellten Reaktionswege sind nur exemplarisch und in einer stark vereinfachten Form dargestellt. So kann nach Bedarf in allen Schritten zusätzlich Base verwendet werden. Weiterhin können die in den einzelnen Synthesestufen genannten Basen durch andere, dem Fachmann bekannte und kommerziell verfügbare Basen, substituiert werden.The reaction pathways shown are only exemplary and presented in a greatly simplified form. So base can be used additionally in all steps as needed. Furthermore, the bases mentioned in the individual synthesis stages can be substituted by other bases known to those skilled in the art and available commercially.

Reaktionsweg A:Reaction path A:

Figure imgb0039
Figure imgb0039
Figure imgb0040
Figure imgb0040
Figure imgb0041
Figure imgb0041

Reaktionsweg B:Pathway B:

Figure imgb0042
Figure imgb0042

Reaktionsweg C:Reaction path C:

Figure imgb0043
Figure imgb0043

Synthese von Ligand 1Synthesis of ligand 1 Reaktionsschema:Scheme:

Figure imgb0044
Figure imgb0044

Einführung der BOC-Gruppe:Introduction of the BOC Group:

Figure imgb0045
Figure imgb0045

In einem 2L Schlenkkolben werden 400 mmol (143,8 g) des 3,3'-Di-tert.-butyl-5,5'-dimethoxy-[1,1'-biphenyl]-2,2'diol und 40 mmol (4,8 g) N,N-Dimethylaminopyridin (DMAP) in 900 mL CH2Cl2 gelöst. Anschließend wurden bei Raumtemperatur 400 mmol (88 g) Di-tert-butyldicarbonat in 280 ml CH2Cl2 gelöst, in einen 500 ml Tropftrichter überführt und innerhalb einer Stunde bei 32 °C zu der Biphenol/DMAP Lösung getropft. Die Lösung wurde über Nacht bei Raumtemperatur gerührt. Am nächsten Morgen wird das Lösungsmittel unter vermindertem Druck entfernt. Der leicht wachsartige, rötliche Rückstand wurde mit 800 ml n-Heptan versetzt und über Nacht gerührt. Dabei erhielt man einen weißen Rückstand, der abfiltriert, zweimal mit 50 ml n-Heptan nachgewaschen und dann getrocknet wurde. Das Zielprodukt konnte als weißer Feststoff (161,6 g, 84%) erhalten werden. 1H-NMR (Tolul-d8): 95% und weitere Verunreinigungen.In a 2L Schlenk flask 400 mmol (143.8 g) of 3,3'-di-tert-butyl-5,5'-dimethoxy- [1,1'-biphenyl] -2,2'diol and 40 mmol (4.8 g) N, N-dimethylaminopyridine (DMAP) dissolved in 900 mL CH 2 Cl 2 . 400 mmol (88 g) of di-tert-butyl dicarbonate were then dissolved in 280 ml of CH 2 Cl 2 at room temperature, transferred to a 500 ml dropping funnel and added dropwise within one hour at 32 ° C. to the biphenol / DMAP solution. The solution was stirred at room temperature overnight. The next morning the solvent is removed under reduced pressure. The slightly waxy, reddish residue was treated with 800 ml of n-heptane and stirred overnight. This gave a white residue, which was filtered off, washed twice with 50 ml of n-heptane and then dried. The target product could be obtained as a white solid (161.6 g, 84%). 1 H-NMR (toluene-d 8 ): 95% and other impurities.

Umsetzung von tert-Butyl-(3,3'-di-tert-butyl-2'-hydroxy-5,5'-dimethoxy-[1,1'-biphenyl]-2-yl)-carbonat mit Phosphortrichlorid:Reaction of tert-butyl (3,3'-di-tert-butyl-2'-hydroxy-5,5'-dimethoxy- [1,1'-biphenyl] -2-yl) carbonate with phosphorus trichloride:

Figure imgb0046
Figure imgb0046

In einem sekurierten 250 ml Schlenkkolben wurden 12 g (0,026 mol) tert-Butyl-(3,3'-di-tert-butyl-2'-hydroxy-5,5'-dimethoxy-[1,1'-biphenyl]-2-yl)-carbonat unter Rühren in 120 ml getrocknetem Toluol und 12,8 ml (0,091 mol) Triethylamin gelöst.In a seked 250 ml Schlenk flask, 12 g (0.026 mol) of tert-butyl (3,3'-di-tert-butyl-2'-hydroxy-5,5'-dimethoxy- [1,1'-biphenyl] - 2-yl) carbonate with stirring in 120 ml of dried toluene and 12.8 ml (0.091 mol) of triethylamine.

In einem zweiten 500 ml Schlenkkolben wurden zunächst 100 ml getrocknetes Toluol mit 8,1 ml (0,091 mol) Phosphortrichlorid verrührt. Anschließend wurde die Phosphortrichlorid-Toluol-Lösung zu der zuvor hergestellten Carbonat-Amin-Toluol-Lösung innerhalb von 30 Minuten bei Raumtemperatur zugetropft. Nach vollständiger Zugabe wurde für 30 Minuten auf 80 °C erwärmt und über Nacht auf Raumtemperatur abgekühlt.In a second 500 ml Schlenk flask, initially 100 ml of dried toluene were stirred with 8.1 ml (0.091 mol) of phosphorus trichloride. Subsequently, the phosphorus trichloride-toluene solution was added dropwise to the previously prepared carbonate-amine-toluene solution within 30 minutes at room temperature. After complete addition was heated to 80 ° C for 30 minutes and cooled to room temperature overnight.

Am nächsten Morgen wurde die Mischung filtriert, mit 50 ml getrocknetem Toluol nachgewaschen und das Filtrat bis zur Trockne eingeengt. Das Zielprodukt konnte als Feststoff (13,1 g, 89%) erhalten werden. 31P-NMR (202,4 MHz, Toluol-d8): 203,2 und 203,3 ppm (100%).The next morning the mixture was filtered, washed with 50 ml of dried toluene and the filtrate concentrated to dryness. The target product could be obtained as a solid (13.1 g, 89%). 31 P-NMR (202.4 MHz, toluene-d 8 ): 203.2 and 203.3 ppm (100%).

Umsetzung von tert-Butyl-3,3'-di-tert-butyl-2'-((dichlorophosphino)oxy)-5,5'-dimethoxy-[1,1'-biphenyl]-2-yl)-carbonat mit 3,3',5,5'-Tetramethyl-(1,1'-biphenyl)-2,2'-diolReaction of tert-butyl-3,3'-di-tert-butyl-2 '- ((dichlorophosphino) oxy) -5,5'-dimethoxy- [1,1'-biphenyl] -2-yl) carbonate with 3,3 ', 5,5'-tetramethyl- (1,1'-biphenyl) -2,2'-diol

Figure imgb0047
Figure imgb0047

In einem sekurierten 1L Schlenkkolben wurden 24,7 g (0,044 mol) tert-Butyl-(3,3'-di-tert-butyl-2'-((dichlorophosphino)oxy)-5,5'-dimethoxy-[1,1'-biphenyl]-2-yl)-carbonat in 400 ml Acetonitril gelöst. In einem zweiten sekurierten Schlenkkolben (1 L) wurden 10,8 g (0,044 mol) 3,3',5,5'-Tetramethyl-(1,1'-biphenyl)-2,2'-diol in 200 ml Acetonitril und 13,1 ml (0,011 mol) getrocknetem Triethylamin unter Rühren gelöst. Anschließend wurde zu der Biphenol-Triethylamin-Lösung langsam die Chlorophosphit-Lösung hinzugetropft und über Nacht gerührt.In a seked 1L Schlenk flask, 24.7 g (0.044 mol) of tert-butyl (3,3'-di-tert-butyl-2 '- ((dichlorophosphino) oxy) -5,5'-dimethoxy- [1, 1'-biphenyl] -2-yl) carbonate dissolved in 400 ml of acetonitrile. In a second recessed Schlenk flask (1 L), 10.8 g (0.044 mol) of 3,3 ', 5,5'-tetramethyl- (1,1'-biphenyl) -2,2'-diol in 200 ml of acetonitrile and Dissolved 13.1 ml (0.011 mol) of dried triethylamine with stirring. Subsequently, the chlorophosphite solution was slowly added dropwise to the biphenol-triethylamine solution and stirred overnight.

Der Ansatz wurde daraufhin filtriert und der Rückstand zweimal mit 15 ml Acetonitril gewaschen. Das Filtrat wurde unter vermindertem Druck eingeengt bis ein Niederschlag ausfiel. Dieser wurde filtriert und getrocknet. Das Zielprodukt konnte als weißer Feststoff (28,5 g, 87%) erhalten werden. 31P-NMR (202,4 MHz,Toluol-d8):139,4 ppm (98,5%).

Figure imgb0048
The reaction was then filtered and the residue washed twice with 15 ml of acetonitrile. The filtrate was concentrated under reduced pressure until a precipitate precipitated. This was filtered and dried. The target product could be obtained as a white solid (28.5 g, 87%). 31 P-NMR (202.4 MHz, toluene-d 8 ): 139.4 ppm (98.5%).
Figure imgb0048

Spektrometer: Bruker Avance 500 MHz FT-Spektrometer
Lösungsmittel: 1,1,2,2-Tetrachlorethan (TCE)
Temperatur: 353K (80°C)
Referenzierung: 1H-NMR, 13C-NMR: TMS = 0
31P-NMR: SR31P = SR1H * (BF31P/BF1H) = SR1H * 0,404807 Tabelle 1: Zuordnung 1H chemische Verschiebungen von 1 δ / ppm Intensität Multiplizität Zuordnung 1,13 9H s 17d (tert-Butyl) 1,20 9H s 20d (O-tert-Butyl) 1,35 9H s 17c (tert-Butyl) 2,02 3H breites-s 7b (Methyl) 2,28 3H s 8b (Methyl) 2,31/2,32 6H breites-s 7a (Methyl) / 8a (Methyl) 3,75 3H s 15c (O-Methyl) 3,78 3H s 15d (O-Methyl) 6,68 1H d 11d 6,83 1H d 11c 6,88 2H (1+1) m 5b, 13d 6,94 1H d 13c 6,96 1H s 5a 6,99 2H (1+1) s 3a + 3b s: Singulett
d: Duplett
t: Triplett
q: Quartett
m: Multiplett Tabelle 2: Zuordnung 13C chemische Verschiebungen von 1 δ / ppm Intensität Gruppe Zuordnung 16,35 1 CH3 7b 16,61 1 CH3 7a 20,66 1 CH3 8b 20,71 1 CH3 8a 27,38 3 CH3 20d 30,27 3 CH3 17d 30,41 3 CH3 17c 34,85 1 Cq 16c 35,02 1 Cq 16d 55,67 1 CH3 15d 55,79 1 CH3 15c 81,67 1 Cq 19d 113,86 1 CH 11c 114,01 1 CH 11d 114,14 1 CH 13c 114,60 1 CH 13d 127,65 1 CH 3b 127,88 1 CH 3a 128,72 1 Cq 10d 130,01 1 Cq 6b 130,77 1 Cq 6a 130,86 1 CH 5b 130,92 1 CH 5a 131,37 1 Cq 2b 131,50 1 Cq 2a 133,49 1 Cq 4b 133,65 1 Cq 4a 135,68 1 Cq 10c 142,09 1 Cq 9d 142,37 1 Cq 14d 143,60 1 Cq 9c 144,05 1 Cq 14c 145,88 1 Cq 1b 146,00 1 Cq 1a 151,27 1 Cq 18d 154,18 1 Cq 12d 157,19 1 Cq 12c Spectrometer: Bruker Avance 500 MHz FT spectrometer
Solvent: 1,1,2,2-tetrachloroethane (TCE)
Temperature: 353K (80 ° C)
Referencing: 1 H-NMR, 13 C-NMR: TMS = 0
31 P-NMR: SR 31P = SR 1H * (BF 31P / BF 1H ) = SR 1H * 0.404807 Table 1: Assignment <sup> 1 </ sup> H chemical shifts of 1 δ / ppm intensity multiplicity assignment 1.13 9H s 17d (tert-butyl) 1.20 9H s 20d (O-tert-butyl) 1.35 9H s 17c (tert-butyl) 2.02 3H wide-s 7b (methyl) 2.28 3H s 8b (methyl) 2.31 / 2.32 6H wide-s 7a (methyl) / 8a (methyl) 3.75 3H s 15c (O-methyl) 3.78 3H s 15d (O-methyl) 6.68 1H d 11d 6.83 1H d 11c 6.88 2H (1 + 1) m 5b, 13d 6.94 1H d 13c 6.96 1H s 5a 6.99 2H (1 + 1) s 3a + 3b s: Singlet
d: doublet
t: triplet
q: Quartet
m: multiplet δ / ppm intensity group assignment 16.35 1 CH 3 7b 16.61 1 CH 3 7a 20.66 1 CH 3 8b 20.71 1 CH 3 8a 27,38 3 CH 3 20d 30.27 3 CH 3 17d 30.41 3 CH 3 17c 34.85 1 C q 16c 35.02 1 C q 16d 55.67 1 CH 3 15d 55.79 1 CH 3 15c 81.67 1 C q 19d 113.86 1 CH 11c 114.01 1 CH 11d 114.14 1 CH 13c 114.60 1 CH 13d 127.65 1 CH 3b 127.88 1 CH 3a 128.72 1 C q 10d 130.01 1 C q 6b 130.77 1 C q 6a 130.86 1 CH 5b 130.92 1 CH 5a 131.37 1 C q 2 B 131.50 1 C q 2a 133.49 1 C q 4b 133.65 1 C q 4a 135.68 1 C q 10c 142.09 1 C q 9d 142.37 1 C q 14d 143.60 1 C q 9c 144.05 1 C q 14c 145.88 1 C q 1b 146.00 1 C q 1a 151.27 1 C q 18d 154.18 1 C q 12d 157.19 1 C q 12c

Synthese von Ligand 2Synthesis of ligand 2 Umsetzung von tert-Butyl-(3,3'-di-tert-butyl-2'-hydroxy-5,5'-dimethoxy-[1,1'-biphenyl]-2-yl)-carbonat mit 2-Chloro-4,4,5,5-tetraphenyl-1,3,2-dioxaphospholanReaction of tert-butyl (3,3'-di-tert-butyl-2'-hydroxy-5,5'-dimethoxy- [1,1'-biphenyl] -2-yl) carbonate with 2-chloro 4,4,5,5-tetraphenyl-1,3,2-dioxaphospholane

Figure imgb0049
Figure imgb0049

In einem sekurierten 250 ml Schlenkkolben wurden 9,1 g (0,021 mol) 2-Chloro-4,4,5,5-tetraphenyl-1,3,2-dioxaphospholan in 75 ml getrocknetem Toluol aufgelöst.In a 250 ml Schlenk flask spiked, 9.1 g (0.021 mol) of 2-chloro-4,4,5,5-tetraphenyl-1,3,2-dioxaphospholane was dissolved in 75 ml of dried toluene.

In einem zweiten Schlenkkolben (250 ml) wurden 9,2 g (0,02 mol) tert-Butyl-(3,3'-di-tert-butyl-2'-hydroxy-5,5'-dimethoxy-[1,1'-biphenyl]-2-yl)-carbonat und 2,3 g (0,02 mol) Kalium-tert.-butylat unter Rühren in 75 ml getrocknetem Toluol gelöst.In a second Schlenk flask (250 ml), 9.2 g (0.02 mol) of tert-butyl (3,3'-di-tert-butyl-2'-hydroxy-5,5'-dimethoxy- [1, 1'-biphenyl] -2-yl) carbonate and 2.3 g (0.02 mol) of potassium tert-butoxide dissolved with stirring in 75 ml of dried toluene.

Anschließend wurde zu der Chlorophosphit-Lösung langsam bei Raumtemperatur die Carbonat-Kalium-tert.-butylat-Toluol-Mischung getropft und über Nacht bei Raumtemperatur gerührt.Subsequently, the carbonate-potassium tert-butoxide-toluene mixture was slowly added dropwise to the chlorophosphite solution at room temperature and stirred overnight at room temperature.

Im Anschluss wurde das Lösungsmittel unter vermindertem Druck entfernt. Der erhaltene Rückstand wurde 5 Stunden in 75 ml getrocknetem Acetonitril gerührt. Der Feststoff wurde filtriert, mit getrocknetem Acetonitril nachgewaschen und getrocknet. Das Zielprodukt konnte als weißer Feststoff (15,3 g, 90%) erhalten werden. 31P-NMR (202,4 MHz, Toluol-d8): 147,0 ppm (99%).

Figure imgb0050
Following this, the solvent was removed under reduced pressure. The resulting residue was stirred for 5 hours in 75 ml of dried acetonitrile. The solid was filtered, washed with dried acetonitrile and dried. The target product could be obtained as a white solid (15.3 g, 90%). 31 P-NMR (202.4 MHz, toluene-d 8 ): 147.0 ppm (99%).
Figure imgb0050

Referenzierung:

  • 1H-NMR: TMS = 0 ppm, 31P-NMR: SR31P = SR1H * (BF31P / BF1H) = SR1H * 0,404807
Tabelle 3: Zuordnung der 13C chemischen Verschiebungen von 2 δ [ppm] Intensität Gruppe Zuordnung 157,31 1 x C Cq C9 155,29 1 x C Cq C16 152,22 1 x C Cq C24 143,68 1 x C Cq C13 143,66/143,54 2 x C Cq C7, C14 143,35 1 x C Cq C6 142,99/142,80 4 x C Cq C2 142,72/142,49 135,65 1 x C Cq C11 132,78 1 x C Cq C12 131,30/130,45 8 x C CH C4 129,66/129,04 127,40-126,90 12 x C CH C3, C5 115,17 1 x C CH C10 114,89 1 x C CH C8 114,83 1 x C CH C15 114,10 1 x C CH C17 95,64/94,85 2 x C Cq C1, C1' 81,32 1 x C Cq C25 55,08 1 x C CH3 C21 55,04 1 x C CH3 C18 35,25 1 x C Cq C19 35,09 1 x C Cq C22 30,77 3 x C CH3 C20 30,64 3 x C CH3 C23 27,56 3 x C CH3 C26 Tabelle 4: Zuordnung der 1H chemischen Verschiebungen von 2 δ [ppm] Intensität Multiplizität Zuordnung 7,54 4H m 7,21 3H m H3,H4,H5 7,09 5H m H8, H10 6,99-6,89 6H m H15, H17 6,83 6H m 3,50 3H s H19 3,41 3H s H22 1,39 9H s H20 1,31 9H s H23 1,21 9H s H26 referencing:
  • 1 H-NMR: TMS = 0 ppm, 31 P-NMR: SR 31P = SR 1H * (BF 31P / BF 1H ) = SR 1H * 0.404807
Table 3: Assignment of the <sup> 13 </ sup> C chemical shifts of 2 δ [ppm] intensity group assignment 157.31 1 x C C q C9 155.29 1 x C C q C16 152.22 1 x C C q C24 143.68 1 x C C q C13 143.66 / 143.54 2 x C C q C7, C14 143.35 1 x C C q C6 142.99 / 142.80 4 x C C q C2 142.72 / 142.49 135.65 1 x C C q C11 132.78 1 x C C q C12 131.30 / 130.45 8 x C CH C4 129.66 / 129.04 127.40 to 126.90 12 x C CH C3, C5 115.17 1 x C CH C10 114.89 1 x C CH C8 114.83 1 x C CH C15 114.10 1 x C CH C17 95.64 / 94.85 2 x C C q C1, C1 ' 81.32 1 x C C q C25 55.08 1 x C CH 3 C21 55.04 1 x C CH 3 C18 35.25 1 x C C q C19 35.09 1 x C C q C22 30.77 3 x C CH 3 C20 30.64 3 x C CH 3 C23 27.56 3 x C CH 3 C26 δ [ppm] intensity multiplicity assignment 7.54 4H m 7.21 3H m H3, H4, H5 7.09 5H m H8, H10 6.99 to 6.89 6H m H15, H17 6.83 6H m 3.50 3H s H19 3.41 3H s H22 1.39 9H s H20 1.31 9H s H23 1.21 9H s H26

Synthese von Ligand 3Synthesis of ligand 3 Umsetzung von tert-Butyl-(3,3'-di-tert-butyl-2'-((dichlorophosphino)oxy)-5,5'-dimethoxy-[1,1'-biphenyl]-2-yl)-carbonat mit 2,2'-BiphenolReaction of tert-butyl- (3,3'-di-tert-butyl-2 '- ((dichlorophosphino) oxy) -5,5'-dimethoxy- [1,1'-biphenyl] -2-yl) carbonate with 2,2'-biphenol

Figure imgb0051
Figure imgb0051

In einem sekurierten 250 ml Schlenkkolben wurden 10,5 g (0,019 mol) tert-Butyl-(3,3'-di-tert-butyl-2'-((dichlorophosphino)oxy)-5,5'-dimethoxy-[1,1'-biphenyl]-2-yl)-carbonat unter Rühren in 50 ml entgastem Acetonitril gelöst.In a 250 ml Schlenk flask spiked, 10.5 g (0.019 mol) of tert-butyl (3,3'-di-tert-butyl-2 '- ((dichlorophosphino) oxy) -5,5'-dimethoxy- [1 , 1'-biphenyl] -2-yl) carbonate dissolved with stirring in 50 ml of degassed acetonitrile.

In einem zweiten sekurierten Schlenkkolben (250 ml) wurden 3,6 g (0,019 mol) 2,2'-Biphenol in 40 ml entgastem Acetonitril und 6,3 ml (0,045 mol) getrocknetem Triethylamin unter Rühren aufgelöst. Anschließend wurde zu der Biphenol-Triethylamin-Lösung langsam bei Raumtemperatur die Chlorophosphit-Mischung hinzugetropft und über Nacht bei Raumtemperatur gerührt. Der erhaltene Feststoff wurde filtriert und getrocknet. Das Zielprodukt konnte als weißer Feststoff (11,5 g, 90%) erhalten werden. 31P-NMR (202,4 MHz, Toluol-d8): 146,2 ppm (100%).

Figure imgb0052
Tabelle 5: Zuordnung der 13C chemischen Verschiebungen von 3 δ [ppm] Intensität Gruppe Zuordnung 157,46 1 x C Cq C16 155,51 1 x C Cq C26 151,76 1 x C Cq C31 150,51/149,92 je 1 x C Cq C1 + C8 144,07 1 x C Cq C24 143,62 1 x C Cq C13 142,70 1 x C Cq C23 142,67 1 x C Cq C14 135,75 1 x C Cq C18 132,13/131,73 1 x C Cq C6 + C7 131,30 1 x C Cq C22 129,87/128,94 je 1 x C CH C5 + C12 128,98/128,91 je 1 x C CH C3 + C10 125,16/124,98 je 1 x C CH C4 + C11 123,54/122,40 je 1 x C CH C2 + C9 115,14 1 x C CH C25 114,93 1 x C CH C15 114,85 1 x C CH C27 114,72 1 x C CH C17 81,36 1 x C Cq C32 55,14 1 x C CH3 C28 55,10 1 x C CH3 C19 35,57 1 x C Cq C29 35,22 1 x C Cq C20 30,78 3 x C CH3 C30 30,62 3 x C CH3 C21 27,45 3 x C CH3 C33 Tabelle 6: Zuordnung der 1H chemischen Verschiebungen von 3 δ [ppm] Intensität Multiplizität Zuordnung 7,26 1H d (J=7,7Hz) 7,15-7,09 6H m H2,H9,H3,H10 7,02 1H t (J=7,7Hz) H5,H12,H15,H25 6,95/6,91 2 x 1H 2 x t (J∼7,5Hz) H4/H 11 6,93 1H d (J=3 Hz) H17 6,87 1H d (J=3 Hz) H27 3,48 3H s H19 3,42 3H s H29 1,50 9H s H20 1,35 9H s H21 1,16 9H s H33 In a second recessed Schlenk flask (250 ml) was dissolved 3.6 g (0.019 mol) of 2,2'-biphenol in 40 ml of degassed acetonitrile and 6.3 ml (0.045 mol) of dried triethylamine with stirring. Subsequently, the chlorophosphite mixture was slowly added dropwise to the biphenol-triethylamine solution at room temperature and stirred overnight at room temperature. The resulting solid was filtered and dried. The target product could be obtained as a white solid (11.5 g, 90%). 31 P-NMR (202.4 MHz, toluene-d 8 ): 146.2 ppm (100%).
Figure imgb0052
 Table 5: Assignment of the <sup> 13 </ sup> C chemical shifts of 3 δ [ppm] intensity group assignment 157.46 1 x C C q C16 155.51 1 x C C q C26 151.76 1 x C C q C31 150.51 / 149.92 each 1 x C C q C1 + C8 144.07 1 x C C q C24 143.62 1 x C C q C13 142.70 1 x C C q C23 142.67 1 x C C q C14 135.75 1 x C C q C18 132.13 / 131.73 1 x C C q C6 + C7 131.30 1 x C C q C22 129.87 / 128.94 each 1 x C CH C5 + C12 128.98 / 128.91 each 1 x C CH C3 + C10 125.16 / 124.98 each 1 x C CH C4 + C11 123.54 / 122.40 each 1 x C CH C2 + C9 115.14 1 x C CH C25 114.93 1 x C CH C15 114.85 1 x C CH C27 114.72 1 x C CH C17 81.36 1 x C C q C32 55.14 1 x C CH 3 C28 55,10 1 x C CH 3 C19 35.57 1 x C C q C29 35.22 1 x C C q C20 30.78 3 x C CH 3 C30 30.62 3 x C CH 3 C21 27.45 3 x C CH 3 C33 δ [ppm] intensity multiplicity assignment 7.26 1H d (J = 7,7Hz) 7.15 to 7.09 6H m H2, H9, H3, H10 7.02 1H t (J = 7.7Hz) H5, H12, H15, H25 6.95 / 6.91 2 x 1H 2 xt (J~7.5Hz) H4 / H 11 6.93 1H d (J = 3 Hz) H17 6.87 1H d (J = 3 Hz) H27 3.48 3H s H19 3.42 3H s H29 1.50 9H s H20 1.35 9H s H21 1.16 9H s H33

Synthese von Ligand 4Synthesis of ligand 4 Umsetzung von tert-Butyl-3,3'-di-tert-butyl-2'-((dichlorophosphino)oxy)-5,5'-dimethoxy-[1,1'-biphenyl]-2-yl)-carbonat mit 3,3,5,5-Tetra-tert.-butyl-biphenolReaction of tert-butyl-3,3'-di-tert-butyl-2 '- ((dichlorophosphino) oxy) -5,5'-dimethoxy- [1,1'-biphenyl] -2-yl) carbonate with 3,3,5,5-tetra-tert-butyl-biphenol

Figure imgb0053
Figure imgb0053

In einem sekurierten 250 ml Schlenkkolben wurden 7.0 g (0,0125 mol) tert-Butyl-(3,3'-di-tert-butyl-2'-((dichlorophosphino)oxy)-5,5'-dimethoxy-[1,1'-biphenyl]-2-yl)-carbonat in 100 ml getrocknetem Acetonitril gelöst.In a seked 250 ml Schlenk flask, 7.0 g (0.0125 mol) of tert-butyl (3,3'-di-tert-butyl-2 '- ((dichlorophosphino) oxy) -5,5'-dimethoxy- [1 , 1'-biphenyl] -2-yl) carbonate dissolved in 100 ml of dried acetonitrile.

In einem zweiten sekurierten Schlenkkolben (100 ml) wurden 5.1 g (0,0125 mol) 3,3',5,5'-Tetra-tert.-butyl-biphenol in 60 ml getrocknetem Acetonitril und 4.2 ml (0,03 mol) getrocknetem Triethylamin unter Rühren aufgelöst. Im Anschluss wurde die Biphenol-Triethylamin-Lösung langsam bei Raumtemperatur zu der Chlorophosphit-Lösung getropft und über Nacht gerührt. Ein Teil des Lösungsmittels wurde unter vermindertem Druck entfernt. Der ausgefallene Feststoff wurde filtriert und getrocknet. Das Zielprodukt konnte als weißer Feststoff (10,2 g, 91%) erhalten werden. 31P-NMR (202,4 MHz, toluene-d8):142,7 ppm (100%).

Figure imgb0054
Tabelle 7: Zuordnung der chemischen Verschiebungen von 4 Nummer δ- 1 H / ppm δ- 13 C / ppm 1 - 151,6 2 - 81,5 3 1,18 27,3 4 - 142,3 5 - 129,9 6|18 6,76 114,7 6,67 114,1 7|17 - 154,4 - 156,8 8|16 6,93 113,5 6,88 115,4 9 - 143,6 10|19 3,78 55,4 3,74 55,7 11 - 35,0 12 1,39 30,6 21|29|31|39|41 1,03 31,2 1.24 31,0 1.29 31,4 1,34 31,5 1,39 30,7 1,48 31,3 13 - 136,4 14 - 142,1 15 - 140,1 20 - 34,6 22|32 - 146,0 146,9 24|34 7,06 126,6 7,30 123,8 25|35 - 145,1 146,3 26|36 7,08 126,3 7,42 124,1 28|38 - 35,1 35,2 30|40 - 34,6 35,4 23|33 - 135,5 132,6 27|37 - 140,0 141,9 In a second recessed Schlenk flask (100 ml), 5.1 g (0.0125 mol) of 3,3 ', 5,5'-tetra-tert-butyl-biphenol in 60 ml of dried acetonitrile and 4.2 ml (0.03 mol) were added. dried triethylamine dissolved with stirring. Thereafter, the biphenol-triethylamine solution was slowly dropped to the chlorophosphite solution at room temperature and stirred overnight. A part of the solvent was removed under reduced pressure. The precipitated solid was filtered and dried. The target product could be obtained as a white solid (10.2 g, 91%). 31 P-NMR (202.4 MHz, toluene-d 8 ): 142.7 ppm (100%).
Figure imgb0054
 Table 7: Allocation of the chemical shifts of <b> 4 </ b> number δ- 1 H / ppm δ- 13 C / ppm 1 - 151.6 2 - 81.5 3 1.18 27.3 4 - 142.3 5 - 129.9 6 | 18 6.76 114.7 6.67 114.1 7 | 17 - 154.4 - 156.8 8 | 16 6.93 113.5 6.88 115.4 9 - 143.6 10 | 19 3.78 55.4 3.74 55.7 11 - 35.0 12 1.39 30.6 21 | 29 | 31 | 39 | 41 1.03 31.2 1.24 31.0 1.29 31.4 1.34 31.5 1.39 30.7 1.48 31.3 13 - 136.4 14 - 142.1 15 - 140.1 20 - 34.6 22 | 32 - 146.0 146.9 24 | 34 7.06 126.6 7.30 123.8 25 | 35 - 145.1 146.3 26 | 36 7.08 126.3 7.42 124.1 28 | 38 - 35.1 35.2 30 | 40 - 34.6 35.4 23 | 33 - 135.5 132.6 27 | 37 - 140.0 141.9

Synthese von Ligand 5Synthesis of ligand 5 Umsetzung von tert-Butyl-3,3'-di-tert-butyl-2'-((dichlorophosphino)oxy)-5,5'-dimethoxy-[1,1'-biphenyl]-2-yl)-carbonat mit 3,3-Di-tert.butyl-5.5-dimethoxy-biphenolReaction of tert-butyl-3,3'-di-tert-butyl-2 '- ((dichlorophosphino) oxy) -5,5'-dimethoxy- [1,1'-biphenyl] -2-yl) carbonate with 3,3-di-tert-butyl-5.5-dimethoxy-biphenol

Figure imgb0055
Figure imgb0055

In einem sekurierten 250 ml Schlenkkolben wurden 7 g (0,0125 mol) tert-Butyl-(3,3'-di-tert-butyl-2'-((dichlorophosphino)oxy)-5,5'-dimethoxy-[1,1'-biphenyl]-2-yl)-carbonat in 100 ml getrocknetem Acetonitril gelöst.In a 250 ml Schlenk flask seked, 7 g (0.0125 mol) of tert-butyl (3,3'-di-tert-butyl-2 '- ((dichlorophosphino) oxy) -5,5'-dimethoxy- [1 , 1'-biphenyl] -2-yl) carbonate dissolved in 100 ml of dried acetonitrile.

In einem zweiten sekurierten Schlenkkolben (100 ml) wurden 4.5 g (0,0125 mol) 3,3-Di-tert.-butyl-5,5-dimethoxy-biphenol in 60 ml getrocknetem Acetonitril und 4.2 ml (0,03 mol) entgastem Triethylamin gelöst. Im Anschluss wurde die Biphenol-Triethylamin-Lösung langsam bei Raumtemperatur zu der Chlorophosphit-Lösung getropft und über Nacht bei Raumtemperatur gerührt.In a second recessed Schlenk flask (100 ml), 4.5 g (0.0125 mol) of 3,3-di-tert-butyl-5,5-dimethoxy-biphenol in 60 ml of dried acetonitrile and 4.2 ml (0.03 mol) were added. degassed triethylamine dissolved. Thereafter, the biphenol-triethylamine solution was slowly dropped to the chlorophosphite solution at room temperature and stirred at room temperature overnight.

Ein Teil des Lösungsmittels wurde unter vermindertem Druck entfernt. Der ausgefallene Feststoff wurde filtriert und getrocknet. Das Zielprodukt konnte als weißer Feststoff (10,5 g, 96%) erhalten werden. 31P-NMR (202,4 MHz, Toluol-d8): 140,9 (95,2%) und weitere Verunreinigungen (weitere Verunreinigungen = P-H-Verbindungen, Oxidverbindungen, noch nicht vollständig umgesetztes Chlorophosphit).A part of the solvent was removed under reduced pressure. The precipitated solid was filtered and dried. The target product could be obtained as a white solid (10.5 g, 96%). 31 P-NMR (202.4 MHz, toluene-d 8 ): 140.9 (95.2%) and other impurities (further impurities = PH compounds, oxide compounds, not yet fully reacted chlorophosphite).

Synthese von Ligand 11Synthesis of ligand 11 Umsetzung von tert-Butyl-(3,3'-di-tert-butyl-2'-((dichlorophosphino)oxy)-5,5'-dimethoxy-[1,1'-biphenyl]-2-yl)-carbonat mit 2,4-DimethylphenolReaction of tert-butyl- (3,3'-di-tert-butyl-2 '- ((dichlorophosphino) oxy) -5,5'-dimethoxy- [1,1'-biphenyl] -2-yl) carbonate with 2,4-dimethylphenol

Figure imgb0056
Figure imgb0056

In einem sekurierten 500 ml Schlenkkolben wurden 6,8 g (0,012 mol) tert-Butyl-(3,3'-di-tert-butyl-2'-((dichlorophosphino)oxy)-5,5'-dimethoxy-[1,1'-biphenyl]-2-yl)-carbonat in 100 ml getrocknetem Acetonitril gelöst.In a seked 500 ml Schlenk flask, 6.8 g (0.012 mol) of tert-butyl (3,3'-di-tert-butyl-2 '- ((dichlorophosphino) oxy) -5,5'-dimethoxy- [1 , 1'-biphenyl] -2-yl) carbonate dissolved in 100 ml of dried acetonitrile.

In einem zweiten sekurierten Schlenkkolben (250 ml) wurden 6 g (6ml; 0,048 mol) 2,4-dimethylphenol in 100 ml getrocknetem Acetonitril und 5 g (7ml; 0.059 mol) entgastem Triethylamin gelöst. Im Anschluss wurde die Biphenol-Triethylamin-Lösung langsam bei Raumtemperatur zu der Chlorophosphit-Lösung getropft und über Nacht bei Raumtemperatur gerührt und am nächsten Morgen im Eisbad gekühlt.In a second recessed Schlenk flask (250 ml) was dissolved 6 g (6 ml, 0.048 mol) of 2,4-dimethylphenol in 100 ml of dried acetonitrile and 5 g (7 ml, 0.059 mol) of degassed triethylamine. Subsequently, the biphenol-triethylamine solution was slowly dripped at room temperature to the chlorophosphite solution and stirred overnight at room temperature and cooled in the ice bath the next morning.

Ein Teil des Lösungsmittels wurde unter vermindertem Druck entfernt Hierbei entstand eine schleimartige Lösung, die nach längerem trocknen zum Feststoff wurde. Das Zielprodukt konnte als weißer Feststoff (11,8 g, 62%) erhalten werden. 31P-NMR (202,4 MHz, Toluol-d8): 139,1 (92,8%) und weitere Verunreinigungen (weitere Verunreinigungen = P-H-Verbindungen, Oxidverbindungen, noch nicht vollständig umgesetztes Chlorophosphit).Part of the solvent was removed under reduced pressure. This gave rise to a mucilaginous solution which, after prolonged drying, became a solid. The target product could be obtained as a white solid (11.8 g, 62%). 31 P-NMR (202.4 MHz, toluene-d 8 ): 139.1 (92.8%) and other impurities (further impurities = PH compounds, oxide compounds, not yet fully reacted chlorophosphite).

Durchführung der KatalyseversucheCarrying out the catalysis experiments Versuchsbeschreibung - allgemeinExperiment description - general

In einem 100 ml-Autoklaven der Fa. Parr Instruments wurde bei verschiedenen Temperaturen, 20 und 50 bar Synthesegasdruck (CO/H2 = 1:1 (Vol-%)) verschiedene Olefine hydroformyliert. Als Precursor wurden bei einer Katalysatorkonzentration von 40 ppm Rh bezogen auf das gesamte Reaktionsgemisch 0.005 g Rh(acac)(CO)2 vorgelegt, bei einer Konzentration von 100 ppm Rh entsprechend 0.0123 g Rh(acac)(CO)2. Als Lösemittel wurden jeweils 40 bis 46 g Toluol verwendet. Der Ligand 1 wurde in unterschiedlichen molaren Überschüssen relativ zum Rhodium verwendet. Zusätzlich wurden als GC-Standard ca. 0.5 g Tetraisopropylbenzol (TIPB) zugefügt. Ca. 6 g Edukt wurden nach Erreichen der vorgesehenen Reaktionstemperatur zudosiert. Während der Reaktion wurde der Druck über eine Synthesegasdosierung mit Massedurchflussmesser und Druckregler konstant gehalten. Die Rührerdrehzahl betrug 1200 min-1. Proben wurden aus der Reaktionsmischung nach 12 Stunden gezogen. Die Ergebnisse der Versuche sind in Tabelle 8 zusammengefasst (Ausbeute = Aldehyd und Alkohol Gesamtausbeute; S = Selektivität zum linearen Produkt).
(acac = acetylacetonat) Tabelle 8: Eintrag Edukt p in [bar] cRh in ppm P: Rh Ausbeute in % S (n-Aldehyd) in % 1 cis-2-Buten 20 40 4 58,0 45,3 2 cis-2-Buten 50 40 4 96,5 40,7 3 1-Buten 20 40 4 49,2 51,9 4 1-Buten 50 40 2 97,4 46,8 5 1-Buten 50 92 8 99,5 50,3 6 1-Octen 50 40 9 97,1 43,2 In a 100 ml autoclave from Parr Instruments, different olefins were hydroformylated at different temperatures, 20 and 50 bar synthesis gas pressure (CO / H 2 = 1: 1 (vol.%)). As precursor at a catalyst concentration of 40 ppm Rh (acac) (CO) 2 were based on the total reaction mixture, 0.005 g of Rh (acac) (CO) 2 presented according 0.0123 g Rh at a concentration of 100 ppm Rh. The solvents used were in each case from 40 to 46 g of toluene. Ligand 1 was used in different molar excess relative to rhodium. In addition, about 0.5 g of tetraisopropylbenzene (TIPB) was added as the GC standard. Approximately 6 g of educt were metered in after reaching the intended reaction temperature. During the reaction, the pressure was kept constant via a synthesis gas metering with mass flow meter and pressure regulator. The stirrer speed was 1200 min -1 . Samples were withdrawn from the reaction mixture after 12 hours. The results of the experiments are summarized in Table 8 (yield = aldehyde and alcohol overall yield, S = selectivity to the linear product).
(acac = acetylacetonate) <u> Table 8: </ u> entry reactant p in [bar] cRh in ppm P: Rh Yield in% S (n-aldehyde) in% 1 cis-2-butene 20 40 4 58.0 45.3 2 cis-2-butene 50 40 4 96.5 40.7 3 1-butene 20 40 4 49.2 51.9 4 1-butene 50 40 2 97.4 46.8 5 1-butene 50 92 8th 99.5 50.3 6 1-octene 50 40 9 97.1 43.2

Reaktionsbedingungen: Ligand 1, Reaktionstemperatur: 120 °CReaction conditions: ligand 1, reaction temperature: 120 ° C

In den Zeilen 1 und 2 sind Versuche zur rhodiumkatalysierten Hydroformylierung des Edukts cis-2-Buten mit dem Liganden 1 gelistet. Bei einem Druck von 20 bar Synthesegas werden in Versuch 1 58,0 mol% Pentanal mit einer Pentanalselektivität von 45,3 % gebildet. Der Anteil der Hydrierung zum Alkan ist mit ca. 1.3 bis 1.5 % niedrig. Die Bildung von Pentanol wird nicht beobachtet. Eine Erhöhung des Synthesegasdruckes führt zu einer Steigerung der Pentanalausbeute auf 95.1 mol-%, die Regioselektivität fällt jedoch auf ca. 40 %.Lines 1 and 2 list attempts for rhodium-catalyzed hydroformylation of the educt cis-2-butene with ligand 1 . At a pressure of 20 bar of synthesis gas, in experiment 1, 58.0 mol% pentanal are formed with a pentane selectivity of 45.3%. The proportion of hydrogenation to the alkane is low at about 1.3 to 1.5%. The formation of pentanol is not observed. An increase in the synthesis gas pressure leads to an increase in the Pentanal yield to 95.1 mol%, the regioselectivity, however, falls to about 40%.

In den Zeilen 3 bis 5 sind Hydroformylierungen von 1-Buten gelistet. Bei 20 bar (Zeile 3) wird bei einem Ligandenüberschuss von 4:1 eine Ausbeute von ca. 49 % und eine Selektivität zum n-Pentanal von ca, 52 % erreicht. Man erhält bei 50 bar Synthesegasdruck eine n-Pentanalselektivität von 50 % bei nahezu vollständigem Umsatz (Zeile 4 und 5). Die Alkanbildung ist niedrig. Im Versuch in Zeile 4 wurde der molare Überschuss des Liganden auf ca. 2:1 vermindert. Die Ausbeute steigt auf 97.4 %, die Pentanalselektivität fällt leicht auf 46.8 %. In Zeile 5 wurde die Rh-Konzentration auf ca. 100 ppm erhöht und der Ligandüberschuss auf 8:1 gegenüber Rhodium erhöht. Die Aldehydausbeute steigt auf 99.5 %, die Regioselektivtät steigt ebenfalls auf 50.3 %.In lines 3 to 5 hydroformylations of 1-butene are listed. At 20 bar (line 3), a yield of about 49% and a selectivity to n-pentanal of about 52% are achieved with a ligand excess of 4: 1. Obtained at 50 bar synthesis gas pressure n-pentanal selectivity of 50% at almost complete conversion (line 4 and 5). The alkane formation is low. In the experiment in line 4, the molar excess of the ligand was reduced to about 2: 1. The yield increases to 97.4%, the pentanal selectivity drops slightly to 46.8%. In line 5, the Rh concentration was increased to about 100 ppm and the ligand excess increased to 8: 1 over rhodium. The aldehyde yield increases to 99.5%, the regioselectivity also increases to 50.3%.

Auch längerkettige Olefine wie 1-Octen lassen sich mit guter n-Selektivität des Produktes hydroformylieren (Zeile 6).Even longer-chain olefins such as 1-octene can be hydroformylated with good n-selectivity of the product (line 6).

Tabelle 9 enthält Versuche zur Hydroformylierung eines n-Octengemischs mit ca. 2 % 1-Octen, 40 % 2-Octenen, 36 % 3-Octenen und 23 % 4-Octenen (Ausbeute = Aldehyd und Alkohol Gesamtausbeute; S = Selektivität zum linearen Produkt n-Pentanal). Hierbei werden die Versuche sowohl mit dem erfindungsgemäßen Liganden 1 als auch mit dem Vergleichsliganden TDTBPP durchgeführt.

Figure imgb0057
Table 9 contains experiments for the hydroformylation of an n-octene mixture with about 2% of 1-octene, 40% of 2-octenes, 36% of 3-octenes and 23% of 4-octenes (yield = aldehyde and alcohol overall yield, S = selectivity to the linear product n-pentanal). In this case, the experiments are carried out both with the ligand 1 according to the invention and with the comparison ligand TDTBPP.
Figure imgb0057

Tris(2,4-di-tert-butylphenyl)phosphit (TDTBPP)Tris (2,4-di-tert-butylphenyl) phosphite (TDTBPP)

Tabelle 9:Table 9: Eintragentry T in [°C]T in [° C] cRh in ppmcRh in ppm P:RhP: Rh Ausbeute in %Yield in% S (lineares Produkt) in %S (linear product) in% 1a 1 a 8080 9090 2020 99,099.0 7,27.2 2a 2 a 8080 9090 55 99,099.0 11,111.1 3a 3 a 9090 9090 2020 99,299.2 10,610.6 4b 4 b 9090 280280 2020 97,997.9 4,74.7 5a 5 a 100100 5050 2020 99,099.0 15,415.4 6b 6 b 100100 9090 2020 96,496.4 6,96.9 7a 7 a 110110 9090 2020 99,299.2 16,516.5 8b 8 b 110110 9090 2020 99,099.0 9,79.7 9a 9 a 120120 9090 2020 95,295.2 22,922.9 10b 10 b 120120 9090 2020 99,099.0 14,414.4 11a 11 a 130130 9090 2020 98,098.0 30,530.5 12b 12 b 130130 7676 2020 98,898.8 23,923.9 13a 13 a 140140 9090 2020 97,497.4 31,631.6 14b 14 b 140140 5656 2020 98,098.0 23,923.9 15a 15 a 120120 9090 44 98,998.9 28,828.8 16a 16 a 120120 4040 9,59.5 98,698.6 29,129.1 17a 17 a 120120 4040 2020 99,199.1 28,228.2

Reaktionsbedingungen: 50 bar Synthesegas (CO/H2) Substrat: n-Octene ;Reaction conditions: 50 bar synthesis gas (CO / H 2 ) Substrate: n-octenes; a): Ligand 1; b): Ligand TDTBPP.a): ligand 1; b): Ligand TDTBPP.

Die Einträge 1 bis 14 zeigen jeweils Ergebnisse von Versuchen bei konstanter Temperatur im Bereich von 80 °C bis 140 °C, und zwar jeweils für den erfindungsgemäßen Liganden 1 als auch für den Vergleichsliganden (TDTBPP). Wie deutlich zu erkennen ist, zeichnet sich der erfindungsgemäße Ligand 1 in allen Fällen durch eine deutlich höhere n-Selektivität zum gewünschten Produkt aus bei sehr guten Gesamtausbeuten. Die Bildung von Alkanen und Alkoholen ist unbedeutend. Vergleicht man die Einträge 13 und 14, so zeigt der Ligand 1 eine um knapp 8 % erhöhte Selektivität im Vergleich zu dem kommerziell verfügbaren Vergleichsliganden. Einträge 15 bis 17 zeigen die Verwendung des Liganden 1 mit unterschiedlichen molaren Überschüssen zu Rhodium. In allen Fällen konnten sehr gute n-Selektivitäten erzielt werden.The entries 1 to 14 respectively show results of tests at constant temperature in the range of 80 ° C to 140 ° C, respectively for the ligand 1 according to the invention as well as for the comparison ligand (TDTBPP). As can be clearly seen, the ligand 1 of the invention is characterized in all cases by a significantly higher n-selectivity to the desired product with very good overall yields. The formation of alkanes and alcohols is insignificant. Comparing entries 13 and 14, ligand 1 shows an almost 8% increased selectivity compared to the commercially available control ligand. Entries 15 to 17 show the use of ligand 1 with different molar excesses to rhodium. In all cases, very good n-selectivities could be achieved.

In Tabelle 10 sind die Ergebnisse für die Hydroformylierung von Di-n-Buten angegeben. Di-n-Buten ist ein Gemisch aus Isomeren von n-Octenen (ca. 16 %), 3-Methyl-heptenen (ca. 65 %) und 3,4-Dimethylhexenen (ca. 19 %) (Ausbeute = Aldehyd und Alkohol Gesamtausbeute; S = Selektivität zum linearen Produkt) . Tabelle 10: Eintrag T in [°C] p in [bar] cRh in ppm P:Rh Ausbeute in % S (nl)* in % 1 120 50 40 10 85,1 30,8 2 120 50 90 7 89,8 28,3 3 120 50 90 7 91,5 30,9 4 120 50 100 5 93,0 36,5 5 120 50 75 20 94,6 29,8 6 130 50 75 20 95,3 32,7 7 110 50 75 20 91,9 24,0 8 120 40 75 20 94,8 29,0 Table 10 gives the results for the hydroformylation of di-n-butene. Di-n-butene is a mixture of isomers of n-octenes (about 16%), 3-methyl-heptenes (about 65%) and 3,4-dimethylhexenes (about 19%) (yield = aldehyde and alcohol Total yield; S = selectivity to linear product). <u> Table 10: </ u> entry T in [° C] p in [bar] cRh in ppm P: Rh Yield in% S (nl) * in% 1 120 50 40 10 85.1 30.8 2 120 50 90 7 89.8 28.3 3 120 50 90 7 91.5 30.9 4 120 50 100 5 93.0 36.5 5 120 50 75 20 94.6 29.8 6 130 50 75 20 95.3 32.7 7 110 50 75 20 91.9 24.0 8th 120 40 75 20 94.8 29.0

Reaktionsbedingungen: Ligand 1; Substrat: Di-n-butenReaction conditions: ligand 1; Substrate: Di-n-butene * Anteil der durch endständige Oxierung entstandenen Aldehyde (im Wesentlichen Nonanal, 4-Methyloctanal, 3-Ethylheptanal, 6-Methyloctanal, 4,5-Dimethylheptanal und 3-Ethyl-4-methyl-hexanal) * Proportion of terminal aldehydes (essentially nonanal, 4-methyloctanal, 3-ethylheptanal, 6-methyloctanal, 4,5-dimethylheptanal and 3-ethyl-4-methyl-hexanal)

Die obige Tabelle 10 enthält Versuchsergebnisse für die rhodiumkatalysierte Hydroformylierung von Di-n-Buten mit dem Liganden 1. Einträge 1 bis 5 wurden bei 120 °C und 50 bar durchgeführt, Eintrag 8 bei 40 bar. Einträge 2 und 3 sind eine Doppelbestimmmung bei einem Ligandüberschuss von 7 zu Rhodium und einer Rhodiumkonzentration bezogen auf das gesamte Reaktionsgemisch von 80 ppm, Eintrag 1 wurde bei einem Überschuss von ca. 10:1 und einer Rh-Konentration von 40 ppm ausgeführt. Eintrag 4 beschreibt eine Verminderung des Überschusses auf 5:1 gegenüber Einträgen 2 und 3. Die Einträge 5 bis 8 sind Versuche mit hohem Ligandüberschuss von ca. 20:1. Einträge 5 bis 7 wurden bei unterschiedlichen Temperaturen durchgeführt. Eintrag 8 unterscheidet sich von Eintrag 5 durch den Druck. Analog zu den Versuchen mit dem n-Octengemisch zeigen sich in den Versuchen 1 bis 6 und 8 durchweg hohe n-Selektivitäten zwischen 28 und 36 mol-%. Bei niedrigerer Temperatur (Eintrag 7) vermindert sich die n-Selektivität auf ca. 24 %. N-Octene werden in der Versuchsdauer von 12 Stunden nahezu quantitativ umgesetzt, der Umsatz der 3-Methyl-Heptene beträgt > 96 %. Die 3,4-Dimethylhexene werden zu 73-86 % umgesetzt. Somit konnte mit Hilfe der obigen Beispiele gezeigt werden, dass das neue Katalysatorsystem auch zur Oxierung von technischen Olefingemischen, die hauptsächlich verzweigte Olefine mit innenständigen Doppelbindungen enthalten, geeignet ist und ein hoher Anteil an gewünschten endständig hydroformylierten Produkten erhalten werden kann.The above Table 10 contains experimental results for the rhodium-catalyzed hydroformylation of di-n-butene with the ligand 1. Entries 1 to 5 were carried out at 120 ° C and 50 bar, entry 8 at 40 bar. Entries 2 and 3 are a double determination with a ligand excess of 7 to rhodium and a rhodium concentration based on the total reaction mixture of 80 ppm, entry 1 was carried out at an excess of about 10: 1 and a Rh concentration of 40 ppm. Entry 4 describes a reduction of the excess to 5: 1 over entries 2 and 3. Entries 5 to 8 are experiments with high ligand excess of about 20: 1. Entries 5 to 7 were carried out at different temperatures. Entry 8 differs from entry 5 by pressure. Analogously to the experiments with the n-octene mixture, high n-selectivities between 28 and 36 mol% are consistently found in experiments 1 to 6 and 8. At lower temperature (entry 7), the n-selectivity decreases to about 24%. N-octenes are used in the experimental period of 12 Hours almost quantitatively implemented, the conversion of 3-methyl-heptene is> 96%. The 3,4-dimethylhexenes are converted to 73-86%. Thus, it has been shown with the aid of the above examples that the novel catalyst system is also suitable for the oxidation of technical olefin mixtures containing mainly branched olefins with internal double bonds and a high proportion of desired terminally hydroformylated products can be obtained.

In Tabelle 11 sind die Ergebnisse für die Hydroformylierung von n-Octenen mit dem Liganden 3 angegeben (Ausbeute = Aldehyd und Alkohol Gesamtausbeute; S = Selektivität zum linearen Produkt). Tabelle 11: Eintrag T in [°C] Ausbeute In % S (lineares Produkt) in % 1 80 30,0 8,6 2 90 85,9 4,9 3 100 91,3 5,9 4 110 98,5 8,3 5 120 99,0 11,9 Table 11 gives the results for the hydroformylation of n-octenes with ligand 3 (yield = aldehyde and alcohol overall yield, S = selectivity to linear product). <u> Table 11: </ u> entry T in [° C] Yield% S (linear product) in% 1 80 30.0 8.6 2 90 85.9 4.9 3 100 91.3 5.9 4 110 98.5 8.3 5 120 99.0 11.9

Reaktionsbedingungen: Ligand 3; 50 bar Synthesegas; Substrat: n-Octene; cRh = 90 ppm; L/Rh = 20;Reaction conditions: ligand 3; 50 bar of synthesis gas; Substrate: n-octenes; cRh = 90 ppm; L / Rh = 20;

Die obige Tabelle enthält eine Zusammenstellung der Versuchsdaten für die Hydroformylierung von n-Octenen mit dem Liganden 3 in Form einer Temperaturreihe von 80 °C bis 120 °C bei 50 bar Synthesegasdruck, einer Rh-Konzentration von ca. 100 ppm und einem Ligandüberschuss von ca. 20:1. Die n-Nonanalselektivitäten sind in dieser Versuchsreihe mit 4.9 bis 11.9 mol-% niedrig, jedoch sind die Aldehydausbeuten bei höheren Temperaturen nahezu quantitativ und sehr gut. Die Alkanbildung ist mit < 1% gering, die Hydrierung zu Alkoholen wird nicht beobachtet.The above table contains a summary of the experimental data for the hydroformylation of n-octenes with the ligand 3 in the form of a temperature range of 80 ° C to 120 ° C at 50 bar synthesis gas pressure, a Rh concentration of about 100 ppm and a ligand excess from about 20: 1. The n-nonane selectivities are low at 4.9 to 11.9 mol% in this series of experiments, but the aldehyde yields are almost quantitative and very good at higher temperatures. The alkane formation is <1% low, the hydrogenation to alcohols is not observed.

In Tabelle 12 sind die Ergebnisse für die Hydroformylierung von Di-n-Buten angegeben. Di-n-Buten ist ein Gemisch aus Isomeren von n-Octenen (ca. 16 %), 3-Methyl-heptenen (ca. 65 %) und 3,4-Dimethylhexenen (ca. 19 %) (Ausbeute = Aldehyd und Alkohol Gesamtausbeute; S = Selektivität zum linearen Produkt) . Tabelle 12: Eintrag Ligand T in [°C] p in [bar] cRh in ppm P:Rh Ausbeute in % 1 4 140 50 100 20:1 38 2 3 140 50 100 10:1 74 3 5 120 50 100 20:1 85 4 5 130 50 100 20:1 86 5 5 140 50 100 20:1 96 6 5 140 50 100 15:1 97 7 5 140 50 100 5:1 97 Table 12 gives the results for the hydroformylation of di-n-butene. Di-n-butene is a mixture of isomers of n-octenes (about 16%), 3-methyl-heptenes (about 65%) and 3,4-dimethylhexenes (about 19%) (yield = aldehyde and alcohol Total yield; S = selectivity to linear product). <u> Table 12: </ u> entry ligand T in [° C] p in [bar] cRh in ppm P: Rh Yield in% 1 4 140 50 100 20: 1 38 2 3 140 50 100 10: 1 74 3 5 120 50 100 20: 1 85 4 5 130 50 100 20: 1 86 5 5 140 50 100 20: 1 96 6 5 140 50 100 15: 1 97 7 5 140 50 100 5: 1 97

Reaktionsbedingungen: Ligand 1; Substrat: Di-n-butenReaction conditions: ligand 1; Substrate: Di-n-butene * Anteil der durch endständige Oxierung entstandenen Aldehyde (im Wesentlichen Nonanal, 4-Methyloctanal, 3-Ethylheptanal, 6-Methyloctanal, 4,5-Dimethylheptanal und 3-Ethyl-4-methyl-hexanal) * Proportion of terminal aldehydes (essentially nonanal, 4-methyloctanal, 3-ethylheptanal, 6-methyloctanal, 4,5-dimethylheptanal and 3-ethyl-4-methyl-hexanal)

Die obige Tabelle 12 enthält Versuchsergebnisse für die rhodiumkatalysierte Hydroformylierung von Di-n-Buten mit den Liganden 3, 4 und 5. Während der Ligand 4 (Eintrag 1) eine moderate Gesamtausbeute an Aldehyden und Alkoholen liefert, zeichnen sich sie Liganden 3 und 4 durch sehr gute Ausbeuten aus. Insbesondere der Ligand 5 zeigt bei erhöhter Temperatur (140°C) nahezu quantitative Umsätze (Einträge 5 bis 7).Table 12 above contains experimental data for the rhodium-catalyzed hydroformylation of di-n-butene with ligands 3, 4 and 5. While ligand 4 (entry 1) provides a moderate overall yield of aldehydes and alcohols, they are characterized by ligands 3 and 4 very good yields. In particular, the ligand 5 shows at elevated temperature (140 ° C) almost quantitative conversions (entries 5 to 7).

Somit konnte mit Hilfe der obigen Beispiele gezeigt werden, dass das neue Katalysatorsystem auch zur Oxierung von technischen Olefingemischen, die hauptsächlich verzweigte Olefine mit innenständigen Doppelbindungen enthalten, geeignet ist und ein hoher Anteil an gewünschten hydroformylierten Produkten erhalten werden kann.Thus, with the aid of the above examples it could be shown that the new catalyst system is also suitable for the oxidation of industrial olefin mixtures containing mainly branched olefins with internal double bonds and a high proportion of desired hydroformylated products can be obtained.

Die erfindungsgemäßen Monophosphitliganden, weisen eine sehr gute n-Selektivität in Bezug auf die Hydroformylierung auf. Die Selektivität zu den gewünschten linearen Aldehyden ist hierbei deutlich größer als beispielsweise bei dem kommerziell verfügbaren Liganden TDTBPP. Die gestellten Aufgaben werden somit durch diese neuartigen, erfindungsgemäßen Liganden gelöst.The monophosphite ligands according to the invention have a very good n-selectivity with respect to the hydroformylation. The selectivity to the desired linear aldehydes here is significantly greater than, for example, in the commercially available ligand TDTBPP. The stated objects are thus achieved by these novel ligands according to the invention.

Claims (15)

Ligand, welcher eine der beiden allgemeinen Strukturen I oder II aufweist:
Figure imgb0058
Figure imgb0059
 wobei
R1, R2, R3, R4, R5, R6, R7, R8 jeweils unabhängig voneinander ausgewählt sind aus: -H, -(C1-C12)-Alkyl, -O-(C1-C12)-Alkyl, -O-(C6-C20)-Aryl, -(C6-C20)-Aryl, Halogen, COO-(C1-C12)-Alkyl, CONH-(C1-C12)-Alkyl, -(C6-C20)-Aryl-CON[(C1-C12)-Alkyl]2, -CO-(C1-C12)-Alkyl, -CO-(C6-C20)-Aryl,-COOH, -OH, -SO3H; -SO3Na, -NO2, -CN, -NH2, -N[(C1-C12)-Alkyl]2;
X und Y jeweils unabhängig voneinander ausgewählt sind aus: -(C1-C12)-Alkyl, -(C6-C20)-Aryl, -(C6-C20)-Aryl-(C1-C12)-Alkyl, -(C6-C20)-Aryl-O-(C1-C12)-Alkyl, -(C1-C12)-Alkyl-(C6-C20)-Aryl, -(C6-C20)-Aryl-COO-(C1-C12)-Alkyl, -(C6-C20)-Aryl-CONH-(C1-C12)-Alkyl,-(C6-C20)-Aryl-CON[(C1-C12)-Alkyl]2, -(C4-C20)-Heteroaryl, -(C4-C20)-Heteroaryl-(C1-C12)-Alkyl,-(C5-C8)-Cycloalkyl-(C4-C20)-Aryl-CO-(C6-C20)-Aryl, Z ausgewählt ist aus: -(C1-C12)-Alkyl-, -(C6-C20)-Aryl-, -(C6-C20)-Aryl-(C1-C12)-Alkyl-, -(C1-C12)-Alkyl-(C6-C20)-Aryl-, -(C4-C20)-Heteroaryl-, -(C6-C20)-Aryl-CO-(C6-C20)-Aryl-, -(C6-C20)-Aryl-(C6-C20)-Aryl-; wobei die genannten Alkyl-, Heteroalkyl-, Cycloalkyl-, Heterocycloalkyl-, Aryl- und Heteroarylgruppen substituiert sein können.Ligand which has one of the two general structures I or II :
Figure imgb0058
Figure imgb0059
 in which
R 1 , R 2 , R 3 , R 4 , R 5 , R 6 , R 7 , R 8 are each independently selected from: -H, - (C 1 -C 12 ) -alkyl, -O- (C 1 -C 12 ) -alkyl, -O- (C 6 -C 20 ) -aryl, - (C 6 -C 20 ) -aryl, halogen, COO- (C 1 -C 12 ) -alkyl, CONH- (C 1 -C 12 ) -alkyl, - (C 6 -C 20 ) -aryl-CON [(C 1 -C 12 ) -alkyl] 2 , -CO- (C 1 -C 12 ) -alkyl, -CO- (C 6 -C 20 ) aryl, -COOH, -OH, -SO 3 H; -SO 3 Na, -NO 2 , -CN, -NH 2 , -N [(C 1 -C 12 ) -alkyl] 2 ;
X and Y are each independently selected from: - (C 1 -C 12 ) -alkyl, - (C 6 -C 20 ) -aryl, - (C 6 -C 20 ) -aryl (C 1 -C 12 ) -alkyl, - (C 6 -C 20 ) -Aryl-O- (C 1 -C 12 ) -alkyl, - (C 1 -C 12 ) -alkyl- (C 6 -C 20 ) -aryl, - (C 6 -C 20 ) -aryl-COO- (C 1 -C 12 ) -alkyl, - (C 6 -C 20 ) -aryl-CONH- (C 1 -C 12 ) -alkyl, - (C 6 -C 20 ) -aryl-CON [(C 1 - C 12 ) alkyl] 2 , - (C 4 -C 20 ) heteroaryl, - (C 4 -C 20 ) heteroaryl (C 1 -C 12 ) alkyl, - (C 5 -C 8 ) cycloalkyl - (C 4 -C 20 ) -aryl-CO- (C 6 -C 20 ) -aryl, Z is selected from: - (C 1 -C 12 ) -alkyl, - (C 6 -C 20 ) -aryl, - (C 6 -C 20 ) -aryl (C 1 -C 12 ) -alkyl, - (C 1 -C 12 ) -alkyl- (C 6 -C 20 ) -aryl, - (C 4 -C 20 ) -heteroaryl, - (C 6 -C 20 ) -aryl-CO- (C 6 -C 20 ) -Aryl, - (C 6 -C 20 ) -aryl (C 6 -C 20 ) -aryl; wherein said alkyl, heteroalkyl, cycloalkyl, heterocycloalkyl, aryl and heteroaryl groups may be substituted. Ligand nach Anspruch 1,
wobei X und Y jeweils unabhängig voneinander ausgewählt sind aus: -(C1-C12)-Alkyl, -(C6-C20)-Aryl, -(C6-C20)-Aryl-(C1-C12)-Alkyl, -(C6-C20)-Aryl-O-(C1-C12)-Alkyl, -(C6-C20)-Aryl-COO-(C1-C12)-Alkyl, -(C6-C20)-Aryl-CONH-(C1-C12)-Alkyl, -(C6-C20)-Aryl-CON[(C1-C12)-Alkyl]2, -(C4-C20)-Heteroaryl, -(C4-C20)-Heteroaryl-(C1-C12)-Alkyl. Ligand according to claim 1,
wherein X and Y are each independently selected from: - (C 1 -C 12 ) -alkyl, - (C 6 -C 20 ) -aryl, - (C 6 -C 20 ) -aryl (C 1 -C 12 ) -alkyl, - (C 6 -C 20 ) -Aryl-O- (C 1 -C 12 ) -alkyl, - (C 6 -C 20 ) -aryl-COO- (C 1 -C 12 ) -alkyl, - (C 6 -C 20 ) -aryl- CONH (C 1 -C 12 ) -alkyl, - (C 6 -C 20 ) -aryl-CON [(C 1 -C 12 ) -alkyl] 2 , - (C 4 -C 20 ) -heteroaryl, - ( C 4 -C 20 ) heteroaryl (C 1 -C 12 ) alkyl. Ligand nach einem der Ansprüche 1 oder 2,
wobei X und Y jeweils unabhängig voneinander ausgewählt sind aus: -(C1-C12)-Alkyl, -(C6-C20)-Aryl, -(C6-C20)-Aryl-(C1-C12)-Alkyl, -(C6-C20)-Aryl-O-(C1-C12)-Alkyl, -(C6-C20)-Aryl-COO-(C1-C12)-Alkyl. Ligand according to one of claims 1 or 2,
wherein X and Y are each independently selected from: - (C 1 -C 12 ) -alkyl, - (C 6 -C 20 ) -aryl, - (C 6 -C 20 ) -aryl (C 1 -C 12 ) -alkyl, - (C 6 -C 20 ) -Aryl-O- (C 1 -C 12 ) -alkyl, - (C 6 -C 20 ) -aryl-COO- (C 1 -C 12 ) -alkyl. Ligand nach einem der Ansprüche 1 bis 3,
wobei Z ausgewählt ist aus: -(C1-C12)-Alkyl-, -(C6-C20)-Aryl-, -(C6-C20)-Aryl-(C1-C12)-Alkyl-, -(C6-C20)-Aryl-CO-(C6-C20)-Aryl-,-(C1-C12)-Alkyl-(C6-C2O)-Aryl-, -(C6-C20)-Aryl-(C6-C20)-Aryl-. Ligand according to one of claims 1 to 3,
where Z is selected from: - (C 1 -C 12 ) -alkyl, - (C 6 -C 20 ) -aryl, - (C 6 -C 20 ) -aryl (C 1 -C 12 ) -alkyl, - (C 6 -C 20 ) -aryl-CO- (C 6 -C 20 ) -aryl, - (C 1 -C 12 ) -alkyl- (C 6 -C 2 O) -aryl, - (C 6 -C 20 ) -Aryl- (C 6 -C 20 ) -Aryl-. Ligand nach einem der Ansprüche 1 bis 4,
wobei R1, R2, R3, R4, R5, R6, R7, R8 jeweils unabhängig voneinander ausgewählt sind aus: -H, - (C1-C12)-Alkyl, -O-(C1-C12)-Alkyl, -O-(C6-C20)-Aryl, -(C6-C20)-Aryl, -COO-(C1-C12)-Alkyl, -CONH-(C1-C12)-Alkyl, -(C6-C20)-Aryl-CON[(C1-C12)-Alkyl]2, -CO-(C1-C12)-Alkyl, -CO-(C6-C20)-Aryl,-COOH, -OH, -NH2, -N[(C1-C12)-Alkyl]2.Ligand according to one of claims 1 to 4,
wherein R 1 , R 2 , R 3 , R 4 , R 5 , R 6 , R 7 , R 8 are each independently selected from: -H, - (C 1 -C 12 ) alkyl, -O- (C C 1 -C 12 ) -alkyl, -O- (C 6 -C 20 ) -aryl, - (C 6 -C 20 ) -aryl, -COO- (C 1 -C 12 ) -alkyl, -CONH- (C 1 -C 12 ) -alkyl, - (C 6 -C 20 ) -aryl-CON [(C 1 -C 12 ) -alkyl] 2 , -CO- (C 1 -C 12 ) -alkyl, -CO- ( C 6 -C 20 ) aryl, -COOH, -OH, -NH 2 , -N [(C 1 -C 12 ) -alkyl] 2 . Ligand nach einem der Ansprüche 1 bis 5,
wobei X und Y für die gleichen Reste stehen.Ligand according to one of claims 1 to 5,
where X and Y are the same radicals. Ligand nach einem der Ansprüche 1 bis 6,
wobei R3 und R6 für -O-(C1-C12)-Alkyl stehen.Ligand according to one of claims 1 to 6,
wherein R 3 and R 6 are -O- (C 1 -C 12 ) alkyl. Ligand nach einem der Ansprüche 1 bis 7,
wobei R3 und R6 für -OMe stehen.Ligand according to one of claims 1 to 7,
wherein R 3 and R 6 are -OMe. Ligand nach einem der Ansprüche 1 bis 8,
wobei R1 und R8 für -(C1-C12)-Alkyl stehen.Ligand according to one of claims 1 to 8,
wherein R 1 and R 8 are - (C 1 -C 12 ) alkyl. Ligand nach einem der Ansprüche 1 bis 9,
wobei R1 und R8 für tert-Butyl stehen.Ligand according to one of claims 1 to 9,
wherein R 1 and R 8 are tert- butyl. Ligand nach einem der Ansprüche 1 bis 10,
welcher die allgemeine Strukturen III aufweist:
Figure imgb0060
 wobei R9, R10, R11, R12, R13, R14, R15, R16 jeweils unabhängig voneinander ausgewählt sind aus: -H, -(C1-C12)-Alkyl, -O-(C1-C12)-Alkyl, -O-(C6-C20)-Aryl, -(C6-C20)-Aryl, -Halogen, -COO-(C1C12)-Alkyl, -CONH-(C1-C12)-Alkyl, -(C6-C20)-Aryl-CON[(C1-C12)-Alkyl]2, -CO-(C1-C12)-Alkyl, -CO-(C6-C20)-Aryl, -COOH, - OH, -SO3H; -SO3Na, -NO2, -CN, -NH2, -N[(C1-C12)-Alkyl]2. Ligand according to one of claims 1 to 10,
which has the general structures III :
Figure imgb0060
 wherein R 9 , R 10 , R 11 , R 12 , R 13 , R 14 , R 15 , R 16 are each independently selected from: -H, - (C 1 -C 12 ) -alkyl, -O- (C 1 -C 12 ) -alkyl, -O- (C 6 -C 20 ) -aryl, - (C 6 -C 20 ) -aryl , -halogen, -COO- (C 1 C 12) alkyl, -CONH- (C 1 -C 12) alkyl, - (C 6 -C 20) -aryl-CON [(C 1 -C 12) - Alkyl] 2 , -CO- (C 1 -C 12 ) -alkyl, -CO- (C 6 -C 20 ) -aryl, -COOH, -OH, -SO 3 H; -SO 3 Na, -NO 2 , -CN, -NH 2 , -N [(C 1 -C 12 ) -alkyl] 2 . Ligand nach einem der Ansprüche 1 bis 11,
welcher die allgemeine Strukturen IV aufweist:
Figure imgb0061
 wobei R9, R10, R11, R12, R13, R14, R15, R16 jeweils unabhängig voneinander ausgewählt sind aus: -H, -(C1-C12)-Alkyl, -O-(C1-C12)-Alkyl, -O-(C6-C20)-Aryl, -(C6-C20)-Aryl, -Halogen, -COO-(C1C12)-Alkyl, -CONH-(C1-C12)-Alkyl, -(C6-C20)-Aryl-CON[(C1-C12)-Alkyl]2, -CO-(C1-C12)-Alkyl, -CO-(C6-C20)-Aryl, -COOH, - OH, -SO3H; -SO3Na, -NO2, -CN, -NH2, -N[(C1-C12)-Alkyl]2. Ligand according to one of claims 1 to 11,
which has the general structures IV :
Figure imgb0061
 wherein R 9 , R 10 , R 11 , R 12 , R 13 , R 14 , R 15 , R 16 are each independently selected from: -H, - (C 1 -C 12 ) -alkyl, -O- (C 1 -C 12 ) -alkyl, -O- (C 6 -C 20 ) -aryl, - (C 6 -C 20 ) -aryl , -halogen, -COO- (C 1 C 12) alkyl, -CONH- (C 1 -C 12) alkyl, - (C 6 -C 20) -aryl-CON [(C 1 -C 12) - Alkyl] 2 , -CO- (C 1 -C 12 ) -alkyl, -CO- (C 6 -C 20 ) -aryl, -COOH, -OH, -SO 3 H; -SO 3 Na, -NO 2 , -CN, -NH 2 , -N [(C 1 -C 12 ) -alkyl] 2 . Komplex umfassend: - einen Liganden nach einem der Ansprüche 1 bis 12, - ein Metallatom ausgewählt aus: Rh, Ru, Co, Ir. Complex comprising: a ligand according to any one of claims 1 to 12, a metal atom selected from: Rh, Ru, Co, Ir. Verwendung eines Liganden nach einem der Ansprüche 1 bis 12,
in einem Ligand-Metall-Komplex zur Katalyse einer Hydroformylierungsreaktion.Use of a ligand according to any one of claims 1 to 12,
in a ligand-metal complex to catalyze a hydroformylation reaction. Verfahren umfassend die Verfahrensschritte: a) Vorlegen eines Olefins, b) Zugabe eines Komplexes nach Anspruch 13,
oder eines Liganden nach einem der Ansprüche 1 bis 12 und einer Verbindung, welche ein Metallatom ausgewählt aus: Rh, Ru, Co, Ir aufweist, c) Zuführen von H2 und CO, d) Erwärmen des Reaktionsgemisches, wobei das Olefin zu einem Aldehyd umgesetzt wird. Method comprising the method steps: a) presentation of an olefin, b) adding a complex according to claim 13,
or a ligand according to any one of claims 1 to 12 and a compound having a metal atom selected from: Rh, Ru, Co, Ir, c) supplying H 2 and CO, d) heating the reaction mixture, wherein the olefin is reacted to an aldehyde.
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